Multifunctional sulfur-containing polymers, compositions thereof and methods of use

ABSTRACT

Disclosed are multifunctional sulfur-containing polymers that are the reaction products of a sulfur-containing diol, a polyol containing at least three hydroxyl groups per polyol molecule, and an aldehyde, a ketone, or a combination thereof. Sealant compositions comprising the multifunctional sulfur-containing polymers are also disclosed.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Continuation of U.S. application Ser. No.14/794,855, filed on Jul. 9, 2015, now Allowed, which is a Continuationof U.S. application Ser. No. 14/656,743, filed on Mar. 13, 2015, nowissued as U.S. Pat. No. 9,109,089, which is a Continuation of U.S.application Ser. No 14/499,293, filed on Sep. 29, 2014, now issued asU.S. Pat. No. 9,012,592, which is a Continuation of U.S. applicationSer. No. 14/177,596, filed on Feb. 11, 2014, now issued as U.S. Pat. No.8,877,887, which is a Division of U.S. application Ser. No. 13/413,143,filed on Mar. 6, 2012, now issued as U.S. Pat. No. 8,729,216, whichclaims benefit under 35 U.S.C. §119(e) of U.S. Provisional ApplicationNo. 61/453,978, filed on Mar. 18, 2011; each of which is incorporated byreference in its entirety.

FIELD

The present disclosure relates to multifunctional sulfur-containingpolymers, compositions comprising multifunctional sulfur-containingpolymers, and methods of using multifunctional sulfur-containingpolymers.

BACKGROUND

Thiol-terminated sulfur-containing polymers are known to be well-suitedfor use in various applications such as aerospace sealant compositions,due, in large part, to their fuel-resistance. Other desirable propertiesfor aerospace sealant compositions include low temperature flexibility,short curing time (the time required to reach a predetermined strength),and elevated-temperature resistance, among others. Sealant compositionsexhibiting at least some of these characteristics and containingthiol-terminated sulfur-containing polymers are described, for example,in U.S. Pat. Nos. 2,466,963, 4,366,307, 4,609,762, 5,225,472, 5,912,319,5,959,071, 6,172,179, 6,232,401, 6,372,849, and 6,509,418. Polysulfidesare also used in aerospace sealant applications where they provide hightensile strength, high shear strength, high-temperature thermalresistance, and fuel resistance, as disclosed, for example in U.S. Pat.No. 7,638,162 and U.S. Publication No. 2005/0245695.

Polythioethers that are liquid at room temperature and pressure and thathave excellent low temperature flexibility and fuel resistance, such asthose disclosed in U.S. Pat. No. 6,172,179, are also useful in aerospacesealant applications. For example, difunctional polythioethers havingterminal hydroxyl groups prepared by reacting a hydroxyl compound withan aldehyde are described, in GB 850,178, U.S. Pat. Nos. 3,290,382,3,959,227, and 3,997,614. Difunctional polythioethers terminated orcapped with isocyanates are also known as disclosed, for example, in GB850,178, and in U.S. Pat. Nos. 3,290,382, 3,959,227, and 3,997,614.Difunctional, i.e., linear, polythioethers, however, often swell uponprolonged exposure to hydrocarbon fuel and other lubricants. On theother hand, sealants made using polyfunctional polythioethers, canexhibit good fuel resistance, hardness and flexibility, but often withcompromised adhesion and elongation.

It is desirable to provide polyfunctional polythioethers that are usefulas fuel resistant and water resistant sealants with improved tensilestrength and elongation, and without compromising adhesion.

SUMMARY

Multifunctional sulfur-containing polymers having enhanced propertiessuitable for aerospace sealant applications are provided.

In a first aspect of the present disclosure, terminal-modifiedsulfur-containing polymers are provided comprising the reaction productsof reactants comprising: (a) a sulfur-containing diol; (b) a polyolcontaining at least three hydroxyl groups per polyol molecule; and (c) areactant selected from an aldehyde, a ketone, and a combination thereof.

In a second aspect of the present disclosure, sulfur-containing polymershaving the structure of Formula (I) are provided:

where each n is an integer selected from 1 to 50; m is an integerselected from 3 to 6; each p is independently selected from 1 and 2;each R¹ is independently selected from C₂₋₆ alkanediyl; each R³ isindependently selected from hydrogen, C₁₋₆ alkyl, C₇₋₁₂ phenylalkyl,substituted C₇₋₁₂ phenylalkyl, C₆₋₁₂ cycloalkylalkyl, substituted C₆₋₁₂cycloalkylalkyl, C₃₋₁₂ cycloalkyl, substituted C₃₋₁₂ cycloalkyl, C₆₋₁₂aryl, and substituted C₆₋₁₂ aryl; and Z represents the core of anm-valent parent polyol Z(OH)_(m).

In a third aspect of the present disclosure, terminal-modifiedsulfur-containing polymers are provided comprising the reaction productsof reactants comprising: (a) a sulfur-containing polymer of Formula (I):

where each n is an integer selected from 1 to 50; m is an integerselected from 3 to 6; each p is independently selected from 1 and 2;each R¹ is independently selected from C₂₋₆ alkanediyl; each R³ isindependently selected from hydrogen, C₁₋₆ alkyl, C₇₋₁₂ phenylalkyl,substituted C₇₋₁₂ phenylalkyl, C₆₋₁₂ cycloalkylalkyl, substituted C₆₋₁₂cycloalkylalkyl, C₃₋₁₂ cycloalkyl, substituted C₃₋₁₂ cycloalkyl, C₆₋₁₂aryl, and substituted C₆₋₁₂ aryl; and Z represents the core of anm-valent parent polyol Z(OH)_(m); and (b) a compound comprising aterminal group selected from a vinyl group, a silyl group, an epoxygroup, and an isocyanate group; and a group that is reactive with thehydroxyl groups of the polymer of Formula (I).

In a fourth aspect of the present disclosure, amine-terminatedsulfur-containing polymers are provided comprising the reaction productsof reactants comprising (a) and (b), wherein: (a) comprises the reactionproducts of reactants comprising (i) and (ii), wherein: (i) comprises asulfur-containing polymer of Formula (I):

where each n is an integer selected from 1 to 50; m is an integerselected from 3 to 6; each p is independently selected from 1 and 2;each R¹ is independently selected from C₂₋₆ alkanediyl; each R³ isindependently selected from hydrogen, C₁₋₆ alkyl, C₇₋₁₂ phenylalkyl,substituted C₇₋₁₂ phenylalkyl, C₆₋₁₂ cycloalkylalkyl, substituted C₆₋₁₂cycloalkylalkyl, C₃₋₁₂ cycloalkyl, substituted C₃₋₁₂ cycloalkyl, C₆₋₁₂aryl, and substituted C₆₋₁₂ aryl; and Z represents the core of anm-valent parent polyol Z(OH)_(m); and (ii) comprises a first compoundselected from a diisocyanate, an activated ethylenically unsaturatedmonoisocyanate, and a tosylate; and (b) comprises a second compoundcomprising an amine group and a group selected from a group that isreactive with an isocyanate group, a group that is reactive with anethylenically unsaturated group, and a group that is reactive with atosylate.

In a fifth aspect of the present disclosure, thiol-terminatedsulfur-containing polymers are provided comprising the reaction productsof reactants comprising (a) and (b), where (a) comprises the reactionproducts of reactants comprising (i) and (ii), wherein: (i) comprises asulfur-containing polymer of Formula (I):

where each n is an integer selected from 1 to 50; m is an integerselected from 3 to 6; each p is independently selected from 1 and 2;each R¹ is independently selected from C₂₋₆ alkanediyl; each R³ isindependently selected from hydrogen, C₁₋₆ alkyl, C₇₋₁₂ phenylalkyl,substituted C₇₋₁₂ phenylalkyl, C₆₋₁₂ cycloalkylalkyl, substituted C₆₋₁₂cycloalkylalkyl, C₃₋₁₂ cycloalkyl, substituted C₃₋₁₂ cycloalkyl, C₆₋₁₂aryl, and substituted C₆₋₁₂ aryl; and Z represents the core of anm-valent parent polyol Z(OH)_(m); and (ii) comprises a first compoundselected from a diisocyanate, thiourea, an ethylenically unsaturatedmonoisocyanate, and a tosylate; and (b) comprises a mercaptoalkanol when(ii) comprises a diisocyanate; a metal hydrosulfide when (ii) comprisesthiourea; a dithiol when (ii) comprises an ethylenically unsaturatedmonoisocyanate; and a metal hydrosulfide when (ii) comprises a tosylate.

In a sixth aspect of the present disclosure, terminal-modifiedsulfur-containing polymers are provided comprising the reaction productsof reactants comprising (a) and (b), wherein: (a) comprises the reactionproducts of reactants comprising (i) and (ii), where (i) comprises asulfur-containing polymer of Formula (I):

where n is an integer selected from 1 to 50; m is an integer selectedfrom 3 to 6; each p is independently selected from 1 and 2; each R¹ isindependently selected from C₂₋₆ alkanediyl; each R³ is independentlyselected from hydrogen, C₁₋₆ alkyl, C₇₋₁₂ phenylalkyl, substituted C₇₋₁₂phenylalkyl, C₆₋₁₂ cycloalkylalkyl, substituted C₆₋₁₂ cycloalkylalkyl,C₃₋₁₂ cycloalkyl, substituted C₃₋₁₂ cycloalkyl, C₆₋₁₂ aryl, andsubstituted C₆₋₁₂ aryl; and Z represents the core of an m-valent parentpolyol Z(OH)_(m); and (ii) comprises a first compound selected from adiisocyanate, an ethylenically unsaturated monoisocyanate, and atosylate; and (b) comprises a second compound comprising a terminalgroup selected from a vinyl group, a silyl group, and an epoxy group;and a group selected from a group that is reactive with an isocyanategroup, a group that is reactive with an ethylenically unsaturated group,and a group that is reactive with a tosylate. In a seventh aspect of thepresent disclosure, terminal-modified sulfur-containing polymers ofFormula (II) are provided:

where each n is an integer selected from 1 to 50; m is an integerselected from 3 to 6; each p is independently selected from 1 and 2;each R¹ is independently selected from C₂₋₆ alkanediyl; each R³ isindependently selected from hydrogen, C₁₋₆ alkyl, C₇₋₁₂ phenylalkyl,substituted C₇₋₁₂ phenylalkyl, C₆₋₁₂ cycloalkylalkyl, substituted C₆₋₁₂cycloalkylalkyl, C₃₋₁₂ cycloalkyl, substituted C₃₋₁₂ cycloalkyl, C₆₋₁₂aryl, and substituted C₆₋₁₂ aryl; each R⁵ is —OR^(5′) wherein R^(5′) isindependently selected from a vinyl-terminated group, a silyl-terminatedgroup, an amine-terminated group, an epoxy-terminated group, athiol-terminated group, and an isocyanate-terminated group; and Zrepresents the core of an m-valent parent polyol Z(OH)_(m). In an eighthaspect of the present disclosure, compositions are provided comprising aterminal-modified sulfur-containing polymer provided by the presentdisclosure and a curing agent that is reactive with theterminal-modified sulfur-containing polymer.

In a ninth aspect of the present disclosure, apertures are provided thatare sealed with a sealant comprising a composition comprising aterminal-modified sulfur-containing polymer provided by the presentdisclosure and a curing agent that is reactive with theterminal-modified sulfur-containing polymer.

The present disclosure is also directed to methods for makingsulfur-containing polymers and compositions thereof, such as sealantcompositions, including aerospace sealant compositions, comprisingsulfur-containing polymers provided by the present disclosure.

DETAILED DESCRIPTION Definitions

A dash (“—”) that is not between two letters or symbols is used toindicate a point of bonding for a substituent or between two atoms. Forexample, —CONH₂ is bonded to another moiety through the carbon atom.

“Activated ethylenically unsaturated monoisocyanate” refers to acompound comprising an ethylenically unsaturated group and amonoisocyanate group in which the double bond is electron deficient suchthat it is activated toward Michael addition, i.e., the double bond is aMichael acceptor.

“Aldehyde” refers to a compound of the formula CH(O)R where R ishydrogen or a hydrocarbon group such as an alkyl group, as definedherein. In certain embodiments, the aldehyde is C₁₋₁₀ aldehyde, C₁₋₆aldehyde, C₁₋₄ aldehyde, C₁₋₃ aldehyde, and in certain embodiments, C₁₋₂aldehyde. In certain embodiments, the aldehyde is formaldehyde. Incertain embodiments of the aldehyde, R is selected from hydrogen, C₁₋₆alkyl, C₇₋₁₂ phenylalkyl, substituted C₇₋₁₂ phenylalkyl, C₆₋₁₂cycloalkylalkyl, substituted C₆₋₁₂ cycloalkylalkyl, C₃₋₁₂ cycloalkyl,substituted C₃₋₁₂ cycloalkyl, C₆₋₁₂ aryl, and substituted C₆₋₁₂ aryl.

“Alkanediyl” refers to a diradical of a saturated, branched orstraight-chain, acyclic hydrocarbon group, having, for example, from 1to 18 carbon atoms (C₁₋₁₈), from 1-14 carbon atoms (C₁₋₁₄), from 1-6carbon atoms (C₁₋₆), from 1 to 4 carbon atoms (C₁₋₄), or from 1 to 3hydrocarbon atoms (C₁₋₃). In certain embodiments, the alkanediyl isC₂₋₁₄ alkanediyl, C₂₋₁₀ alkanediyl, C₂₋₈ alkanediyl, C₂₋₆ alkanediyl,C₂₋₄ alkanediyl, and in certain embodiments, C₂₋₃ alkanediyl. Examplesof alkanediyl groups include methane-diyl (—CH₂—), ethane-1,2-diyl(—CH₂CH₂—), propane-1,3-diyl and iso-propane-1,2-diyl (e.g., —CH₂CH₂CH₂—and —CH(CH₃)CH₂—), butane-1,4-diyl (—CH₂CH₂CH₂CH₂—), pentane-1,5-diyl(—CH₂CH₂CH₂CH₂CH₂—), hexane-1,6-diyl (—CH₂CH₂CH₂CH₂CH₂CH₂—),heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl,dodecane-1,12-diyl, and the like.

“Alkanedithiol” refers to an alkane group in which two of the hydrogenatoms are replaced with a thiol group, —SH. In certain embodiments, thealkanedithiol is C₂₋₁₂ alkanedithiol, C₂₋₁₀ alkanedithiol, C₂₋₈alkanedithiol, C₂₋₆ alkanedithiol, and in certain embodiments, C₂₋₃alkanedithiol.

“Alkanearene” refers to a hydrocarbon group having one or more aryland/or arenediyl groups and one or more alkyl and/or alkanediyl groups,where aryl, arenediyl, alkyl, and alkanediyl are defined here. Incertain embodiments, each aryl and/or arenediyl group(s) is C₆₋₁₂,C₆₋₁₀, and in certain embodiments, phenyl or benzenediyl. In certainembodiments, each alkyl and/or alkanediyl group(s) is C₁₋₆, C₁₋₄, C₁₋₃,and in certain embodiments, methyl, methanediyl, ethyl, orethane-1,2-diyl. In certain embodiments, the alkanearene group is C₄₋₁₈alkanearene, C₄₋₁₆ alkanearene, C₄₋₁₂ alkanearene, C₄₋₈ alkanearene,C₆₋₁₂ alkanearene, C₆₋₁₀ alkanearene, and in certain embodiments, C₆₋₉alkanearene. Examples of alkanearene groups include diphenyl methane.

“Alkanearenediyl” refers to a diradical of an alkanearene group. Incertain embodiments, the alkanearenediyl group is C₄₋₁₈ alkanearenediyl,C₄₋₁₆ alkanearenediyl, C₄₋₁₂ alkanearenediyl, C₄₋₈ alkanearenediyl,C₆₋₁₂ alkanearenediyl, C₆₋₁₀ alkanearenediyl, and in certainembodiments, C₆₋₉ alkanearenediyl. Examples of alkanearenediyl groupsinclude diphenyl methane-4,4′-diyl.

“Alkanecycloalkane” refers to a saturated hydrocarbon group having oneor more cycloalkyl and/or cycloalkanediyl groups and one or more alkyland/or alkanediyl groups, where cycloalkyl, cycloalkanediyl, alkyl, andalkanediyl are defined herein. In certain embodiments, each cycloalkyland/or cycloalkanediyl group(s) is C₃₋₆, C₅₋₆, and in certainembodiments, cyclohexyl or cyclohexanediyl. In certain embodiments, eachalkyl and/or alkanediyl group(s) is C₁₋₆, C₁₋₄, C₁₋₃, and in certainembodiments, methyl, methanediyl, ethyl, or ethane-1,2-diyl. In certainembodiments, the alkanecycloalkane group is C₄₋₁₈ alkanecycloalkane,C₄₋₁₆ alkanecycloalkane, C₄₋₁₂ alkanecycloalkane, C₄₋₈alkanecycloalkane, C₆₋₁₂ alkanecycloalkane, C₆₋₁₀ alkanecycloalkane, andin certain embodiments, C₆₋₉ alkanecycloalkane. Examples ofalkanecycloalkane groups include 1,1,3,3-tetramethylcyclohexane andcyclohexylmethane.

“Alkanecycloalkanediyl” refers to a diradical of an alkanecycloalkanegroup. In certain embodiments, the alkanecycloalkanediyl group is C₄₋₁₈alkanecycloalkanediyl, C₄₋₁₆ alkanecycloalkanediyl, C₄₋₁₂alkanecycloalkanediyl, C₄₋₈ alkanecycloalkanediyl, C₆₋₁₂alkanecycloalkanediyl, C₆₋₁₀ alkanecycloalkanediyl, and in certainembodiments, C₆₋₉ alkanecycloalkanediyl. Examples ofalkanecycloalkanediyl groups include1,1,3,3-tetramethylcyclohexane-1,5-diyl and cyclohexylmethane-4,4′-diyl.

“Alkoxy” refers to a —OR group where R is alkyl as defined herein.Examples of alkoxy groups include methoxy, ethoxy, n-propoxy,isopropoxy, and n-butoxy. In certain embodiments, the alkoxy group isC₁₋₈ alkoxy, C₁₋₆ alkoxy, C₁₋₄ alkoxy, and in certain embodiments, C₁₋₃alkoxy.

“Alkyl” refers to a monoradical of a saturated, branched orstraight-chain, acyclic hydrocarbon group having, for example, from 1 to20 carbon atoms, from 1 to 10 carbon atoms, from 1 to 6 carbon atoms,from 1 to 4 carbon atoms, or from 1 to 3 carbon atoms. Examples of alkylgroups include methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl,tert-butyl, n-hexyl, n-decyl, tetradecyl, and the like. In certainembodiments, the alkyl group is C₂₋₆ alkyl, C₂₋₄ alkyl, and in certainembodiments, C₂₋₃ alkyl.

“Aminoalkyl” refers to an alkyl group, as defined herein, in which oneof the hydrogen atoms of the alkyl group is replaced with an aminogroup, —NH₂. In certain embodiments, the aminoalkyl group is C₁₋₁₀aminoalkyl, C₁₋₆ aminoalkyl, C₁₋₄ aminoalkyl, C₁₋₃ aminoalkyl, and incertain embodiments, C₁₋₂ aminoalkyl.

“Arenediyl” refers to diradical monocyclic or polycyclic aromatic group.Examples of arenediyl groups include benzene-diyl and naphthalene-diyl.In certain embodiments, the arenediyl group is C₆₋₁₂ arenediyl, C₆₋₁₀arenediyl, C₆₋₉ arenediyl, and in certain embodiments, benzene-diyl.

“Aryl” refers to a monovalent aromatic hydrocarbon radical derived bythe removal of one hydrogen atom from a single carbon atom of a parentaromatic ring system. Aryl encompasses 5- and 6-membered carbocyclicaromatic rings, for example, benzene; bicyclic ring systems wherein atleast one ring is carbocyclic and aromatic, for example, naphthalene,indane, and tetralin; and tricyclic ring systems wherein at least onering is carbocyclic and aromatic, for example, fluorene. Arylencompasses multiple ring systems having at least one carbocyclicaromatic ring fused to at least one carbocyclic aromatic ring,cycloalkyl ring, or heterocycloalkyl ring. For example, aryl includes 5-and 6-membered carbocyclic aromatic rings fused to a 5- to 7-memberedheterocycloalkyl ring containing one or more heteroatoms chosen from N,O, and S. For such fused, bicyclic ring systems wherein only one of therings is a carbocyclic aromatic ring, the point of attachment may be atthe carbocyclic aromatic ring or the heterocycloalkyl ring. Examples ofaryl groups include, but are not limited to, groups derived fromaceanthrylene, acenaphthylene, acephenanthrylene, anthracene, azulene,benzene, chrysene, coronene, fluoranthene, fluorene, hexacene,hexaphene, hexalene, as-indacene, s-indacene, indane, indene,naphthalene, octacene, octaphene, octalene, ovalene, penta-2,4-diene,pentacene, pentalene, pentaphene, perylene, phenalene, phenanthrene,picene, pleiadene, pyrene, pyranthrene, rubicene, triphenylene,trinaphthalene, and the like. In certain embodiments, the aryl group canhave from 6 to 20 carbon atoms, and in certain embodiments, from 6 to 12carbon atoms. Aryl, however, does not encompass or overlap in any waywith heteroaryl, separately defined herein. Hence, a multiple ringsystem in which one or more carbocyclic aromatic rings is fused to aheterocycloalkyl aromatic ring, is heteroaryl, not aryl, as definedherein. In certain embodiments, an aryl group is phenyl.

“Arylalkyl” refers to an alkyl group in which one of the hydrogen atomsis replaced with an aryl group. In certain embodiments of an arylalkylgroup, a hydrogen atom on the terminal carbon atom of an alkyl group isreplaced with an aryl group. In certain embodiments of arylalkyl, thearyl group is a C₆₋₁₂ aryl group, in certain embodiments a C₆₋₁₀ arylgroup, and in certain embodiments, a phenyl or naphthyl group. Incertain embodiments, the alkanediyl portion of an arylalkyl group maybe, for example, C₁₋₁₀ alkanediyl, C₁₋₆ alkanediyl, C₁₋₄ alkanediyl,C₁₋₃ alkanediyl, propane-1,3-diyl, ethane-1,2-diyl, or methane-diyl. Incertain embodiments, the arylalkyl group is C₇₋₁₈ arylalkyl, C₇₋₁₆arylalkyl, C₇₋₁₂ arylalkyl, C₇₋₁₀ arylalkyl, or C₇₋₉ arylalkyl. Forexample, C₇₋₉ arylalkyl can include a C₁₋₃ alkyl group bonded to aphenyl group.

“Cycloalkanediyl” refers to a diradical saturated monocyclic orpolycyclic hydrocarbon group. In certain embodiments, thecycloalkanediyl group is C₃₋₁₂ cycloalkanediyl, C₃₋₈ cycloalkanediyl,C₃₋₆ cycloalkanediyl, and in certain embodiments, C₅₋₆ cycloalkanediyl.Examples of cycloalkanediyl groups include cyclohexane-1,4-diyl,cyclohexane-1,3-diyl, and cyclohexane-1,2-diyl.

“Cycloalkyl” refers to a saturated monocyclic or polycyclic hydrocarbonmonoradical group. In certain embodiments, the cycloalkyl group is C₃₋₁₂cycloalkyl, C₃₋₈ cycloalkyl, C₃₋₆ cycloalkyl, and in certainembodiments, C₅₋₆ cycloalkyl.

“Cycloalkylalkyl” refers to an alkyl group in which one of the hydrogenatoms is replaced with a cycloalkyl group. In certain embodiments of thecycloalkylalkyl group, a hydrogen atom on the terminal carbon atom of analkyl group is replaced with a cycloalkyl group. In certain embodimentsof cycloalkylalkyl, the cycloalkyl group is a C₃₋₆ cycloalkyl group, incertain embodiments a C₅₋₆ cycloalkyl group, and in certain embodiments,a cyclopropyl, a cyclobutyl, a cyclopentyl, or a cyclohexyl group. Incertain embodiments, the alkanediyl portion of a cycloalkylalkyl groupmay be, for example, C₁₋₁₀ alkanediyl, C₁₋₆ alkanediyl, C₁₋₄ alkanediyl,C₁₋₃ alkanediyl, propane-1,3-diyl, ethane-1,2-diyl, or methane-diyl. Incertain embodiments, the cycloalkylalkyl group is C₄₋₁₆ cycloalkylalkyl,C₄₋₁₂ cycloalkylalkyl, C₄₋₁₀ cycloalkylalkyl, C₆₋₁₂ cycloalkylalkyl, orC₆₋₉ cycloalkylalkyl. For example, C₆₋₉ cycloalkylalkyl includes a C₁₋₃alkyl group bonded to a cyclopentyl or a cyclohexyl group.

“Cycloalkylalkanediyl” refers to a diradical of a cycloalkylalkanegroup. In certain embodiments, the cycloalkylalkanediyl group is C₄₋₁₆cycloalkylalkanediyl, C₄₋₁₂ cycloalkylalkanediyl, C₄₋₁₀cycloalkylalkanediyl, C₆₋₁₂ cycloalkylalkanediyl, or C₆₋₉cycloalkylalkanediyl. For example, C₆₋₉ cycloalkylalkanediyl includes aC₁₋₃ alkyl group bonded to a cyclopentyl or a cyclohexyl group.

“Cycloalkylalkane” group refers to a saturated, branched orstraight-chain, acyclic hydrocarbon group in which one of the hydrogenatoms is replaced with a cycloalkane group. In certain embodiments ofthe cycloalkylalkane group, a hydrogen atom on the terminal carbon atomof a linear alkane group is replaced with a cycloalkyl group. In certainembodiments the cycloalkyl group is a C₃₋₆ cycloalkyl group, in certainembodiments a C₅₋₆ cycloalkyl group, and in certain embodiments acyclopropyl, a cyclobutyl, a cyclopentyl, or a cyclohexyl group. Thealkane portion of a cycloalkylalkane group may be, for example, C₁₋₁₀alkane, C₁₋₆ alkane, C₁₋₄ alkane, C₁₋₃ alkane, propane, ethane, ormethane. In certain embodiments, a cycloalkylalkane group is C₄₋₁₆cycloalkylalkane, C₄₋₁₂ cycloalkylalkane, C₄₋₁₀ cycloalkylalkane, C₆₋₁₂cycloalkylalkane, or C₆₋₉ cycloalkylalkane For example, C₆₋₉cycloalkylalkane includes a C₁₋₃ alkyl group bonded to a cyclopentyl ora cyclohexyl group.

“Group derived from a diisocyanate” refers to a group in which one orboth of the terminal isocyanate groups of a parent diisocyanate form aurethane (—O—C(O)—NR—), thiourethane (—S—C(O)—NR—), or urea(—NR—C(O)—NR—) linkage, where R is hydrogen or a hydrocarbon group. Thegroup derived from a diisocyanate includes groups derived from aliphaticdiisocyanates and groups derived from aromatic diisocyanates. In certainembodiments, the group derived from a diisocyanate is a group derivedfrom an aliphatic diisocyanate, and in certain embodiments a groupderived from a diisocyanate is a group derived from an aromaticdiisocyanate. For example, a compound derived from2,6-diisocyanatotoluene has the structure:

where each R is a bond to a —O—, —S—, or —NR— group.

Examples of aliphatic diisocyanates include, 1,6-hexamethylenediisocyanate, 1,5-diisocyanato-2-methylpentane,methyl-2,6-diisocyanatohexanoate, bis(isocyanatomethyl)cyclohexane,1,3-bis(isocyanatomethyl)cyclohexane, 2,2,4-trimethylhexane1,6-diisocyanate, 2,4,4-trimethylhexane 1,6-diisocyanate,2,5(6)-bis(isocyanatomethyl)cyclo[2.2.1]heptane,1,3,3-trimethyl-1-(isocyanatomethyl)-5-isocyanatocyclohexane,1,8-diisocyanato-2,4-dimethyloctane,octahydro-4,7-methano-1H-indenedimethyl diisocyanate, and1,1′-methylenebis(4-isocyanatocyclohexane), and 4,4-methylenedicyclohexyl diisocyanate (H₁₂MDI). Examples of aromatic diisocyanatesinclude 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate,2,6-toluene diisocyanate (2,6-TDI), 2,4-toluene diisocyanate (2,4-TDI),a blend of 2,4-TDI and 2,6-TDI, 1,5-diisocyanatonaphthalene, diphenyloxide 4,4′-diisocyanate, 4,4′-methylenediphenyl diisocyanate (4,4-MDI),2,4′-methylenediphenyl diisocyanate (2,4-MDI),2,2′-diisocyanatodiphenylmethane (2,2-MDI), diphenylmethane diisocyanate(MDI), 3,3′-dimethyl-4,4′-biphenylene isocyanate,3,3′-dimethoxy-4,4′-biphenylene diisocyanate,1-[(2,4-diisocyanatophenyl)methyl]-3-isocyanato-2-methyl benzene, and2,4,6-triisopropyl-m-phenylene diisocyanate.

Examples of alicyclic diisocyanates from which the diisocyanates may beselected include isophorone diisocyanate (IPDI), cyclohexanediisocyanate, methylcyclohexane diisocyanate,bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane,bis(isocyanatocyclohexyl)-2,2-propane,bis(isocyanatocyclohexyl)-1,2-ethane,2-isocyanatomethyl-3-(3-isocyanatopropyl)-5-isocyanatomethyl-bicyclo[2.2.1]-heptane,2-isocyanatomethyl-3-(3-isocyanatopropyl)-6-isocyanatomethyl-bicyclo[2.2.1]-heptane,2-isocyanatomethyl-2-(3-isocyanatopropyl)-5-isocyanatomethyl-bicyclo[2.2.1]-heptane,2-isocyanatomethyl-2-(3-isocyanatopropyl)-6-isocyanatomethyl-bicyclo[2.2.1]-heptane,2-isocyanatomethyl-3-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)-bicyclo[2.2.1]-heptane,2-isocyanatomethyl-2-(3-isocyanatopropyl)-5-(2-isocyanatoethyl)-bicyclo[2.2.1]-heptane,and2-isocyanatomethyl-2-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)-bicyclo[2.2.1]-heptane.

Examples of aromatic diisocyanates in which the isocyanate groups arenot bonded directly to the aromatic ring include, but are not limitedto, bis(isocyanatoethyl)benzene, α, α, α′,α′-tetramethylxylenediisocyanate, 1,3-bis(1-isocyanato-1-methylethyl)benzene,bis(isocyanatobutyl)benzene, bis(isocyanatomethyl)naphthalene,bis(isocyanatomethyl)diphenyl ether, bis(isocyanatoethyl)phthalate, and2,5-di(isocyanatomethyl)furan. Aromatic diisocyanates having isocyanategroups bonded directly to the aromatic ring include phenylenediisocyanate, ethylphenylene diisocyanate, isopropylphenylenediisocyanate, dimethylphenylene diisocyanate, diethylphenylenediisocyanate, diisopropylphenylene diisocyanate, naphthalenediisocyanate, methylnaphthalene diisocyanate, biphenyl diisocyanate,4,4′-diphenylmethane diisocyanate,bis(3-methyl-4-isocyanatophenyl)methane, bis(isocyanatophenyl)ethylene,3,3′-dimethoxy-biphenyl-4,4′-diisocyanate, diphenylether diisocyanate,bis(isocyanatophenylether)ethyleneglycol,bis(isocyanatophenylether)-1,3-propyleneglycol, benzophenonediisocyanate, carbazole diisocyanate, ethylcarbazole diisocyanate,dichlorocarbazole diisocyanate, 4,4′-diphenylmethane diisocyanate,p-phenylene diisocyanate, 2,4-toluene diisocyanate, and 2,6-toluenediisocyanate.

“Group derived from an ethylenically unsaturated monoisocyanate” refersto a group in which the isocyanate group of a parent ethylenicallyunsaturated monoisocyanate forms a urethane, thiourethane or urealinkage and the ethylenically unsaturated group is bonded to anothermoiety or that is not bonded to another moiety. In certain embodiments,a group derived from an ethylenically unsaturated isocyanate refers to agroup in which an isocyanate group of a parent ethylenically unsaturatedmonoisocyanate forms a urethane, thiourethane or urea linkage and theethylenically unsaturated group is not bonded to another moiety. Forexample, a group derived from the ethylenically unsaturatedmonoisocyanate 2-isocyanatoethyl methacrylate can have the structure:

where the carbonyl is bonded to —O—, —S—, or —NR— to form a urethane,thiourethane or urea group, respectively. In certain embodiments, agroup derived from an ethylenically unsaturated isocyanate refers to agroup in which an isocyanate group of a parent ethylenically unsaturatedmonoisocyanate forms a urethane, thiourethane or urea linkage and theethylenically unsaturated group is bonded to another moiety. In suchembodiments, a group derived from the ethylenically unsaturatedmonoisocyanate 2-isocyanatoethyl methacrylate has the structure:

where the carbonyl is bonded to —O—, —S—, or —NR— to form a urethane,thiourethane or urea group, and the former vinyl group is bonded toanother moiety.

“Heteroalkanearene” refers to an alkanearene group in which one or moreof the carbon atoms are replaced with a heteroatom, such as N, O, S, orP. In certain embodiments of heteroalkanearene, a heteroatom is selectedfrom N and O.

“Heteroalkanearenediyl” refers to an alkanearenediyl group in which oneor more of the carbon atoms are replaced with a heteroatom, such as N,O, S, or P. In certain embodiments of heteroalkanearenediyl, theheteroatom is selected from N and O.

“Heteroalkanecycloalkane” refers to an alkanecycloalkane group in whichone or more of the carbon atoms are replaced with a heteroatom, such asN, O, S, or P. In certain embodiments of heteroalkanecycloalkane, theheteroatom is selected from N and O.

“Heteroalkanecycloalkanediyl” refers to an alkanecycloalkanediyl groupin which one or more of the carbon atoms are replaced with a heteroatom,such as N, O, S, or P. In certain embodiments ofheteroalkanecycloalkanediyl, the heteroatom is selected from N and O.

“Heteroalkanediyl” refers to an alkanediyl group in which one or more ofthe carbon atoms are replaced with a heteroatom, such as N, O, S, or P.In certain embodiments of heteroalkanediyl, the heteroatom is selectedfrom N and O.

“Heterocycloalkanediyl” refers to a cycloalkanediyl group in which oneor more of the carbon atoms are replaced with a heteroatom, such as N,O, S, or P. In certain embodiments of heterocycloalkanediyl, theheteroatom is selected from N and O.

“Heteroalkyl” refers to an alkyl group in which one or more of thecarbon atoms are replaced with a heteroatom, such as N, O, S, or P. Incertain embodiments of heteroalkyl, the heteroatom is selected from Nand O.

“Heteroarenediyl” refers to an arenediyl group in which one or more ofthe carbon atoms are replaced with a heteroatom, such as N, O, S, or P.In certain embodiments of heteroarenediyl, the heteroatom is selectedfrom N and O.

“Heteroaryl” refers to a monovalent heteroaromatic radical derived bythe removal of one hydrogen atom from a single atom of a parentheteroaromatic ring system. Heteroaryl encompasses multiple ring systemshaving at least one heteroaromatic ring fused to at least one otherring, which can be aromatic or non-aromatic. Heteroaryl encompasses 5-to 7-membered aromatic, monocyclic rings containing one or more, forexample, from 1 to 4, or in certain embodiments, from 1 to 3,heteroatoms chosen from N, O, S, and P with the remaining ring atomsbeing carbon; and bicyclic heterocycloalkyl rings containing one ormore, for example, from 1 to 4, or in certain embodiments, from 1 to 3,heteroatoms chosen from N, O, S, and P, with the remaining ring atomsbeing carbon and wherein at least one heteroatom is present in anaromatic ring. For example, heteroaryl includes a 5- to 7-memberedheteroaromatic ring fused to a 5- to 7-membered cycloalkyl ring. Forsuch fused, bicyclic heteroaryl ring systems wherein only one of therings contains one or more heteroatoms, the point of attachment may beat the heteroaromatic ring or the cycloalkyl ring. In certainembodiments, where the total number of N, O, S, and P atoms in theheteroaryl group exceeds one, the heteroatoms are not adjacent to oneanother. In certain embodiments, the total number of N, O, S, and Patoms in the heteroaryl group is not more than two. In certainembodiments, the total number of N, O, S, and P atoms in the aromaticheterocycle is not more than one. Heteroaryl does not encompass oroverlap with aryl as defined herein. Examples of heteroaryl groupsinclude, but are not limited to, groups derived from acridine,arsindole, carbazole, α-carboline, chromane, chromene, cinnoline, furan,imidazole, indazole, indole, indoline, indolizine, isobenzofuran,isochromene, isoindole, isoindoline, isoquinoline, isothiazole,isoxazole, naphthyridine, oxadiazole, oxazole, perimidine,phenanthridine, phenanthroline, phenazine, phthalazine, pteridine,purine, pyran, pyrazine, pyrazole, pyridazine, pyridine, pyrimidine,pyrrole, pyrrolizine, quinazoline, quinoline, quinolizine, quinoxaline,tetrazole, thiadiazole, thiazole, thiophene, triazole, xanthene, and thelike. In certain embodiments, a heteroaryl group is C₅₋₂₀ heteroaryl,C₅₋₁₂ heteroaryl, C₅₋₁₀ heteroaryl, and in certain embodiments C₅₋₆heteroaryl. In certain embodiments heteroaryl groups are derived fromthiophene, pyrrole, benzothiophene, benzofuran, indole, pyridine,quinoline, imidazole, oxazole, or pyrazine.

“Ketone” refers to a compound of the formula CO(R)₂ where each R is ahydrocarbon group. In certain embodiments of a ketone, each R isindependently selected from C₁₋₆ alkyl, C₇₋₁₂ phenylalkyl, substitutedC₇₋₁₂ phenylalkyl, C₆₋₁₂ cycloalkylalkyl, and substituted C₆₋₁₂cycloalkylalkyl. In certain embodiments of the ketone, each R isindependently selected from methyl, ethyl, and propyl. In certainembodiments, the ketone is selected from propan-2-one, butan-2-one,pentan-2-one, and pentan-3-one. In certain embodiments of the ketone,each R is independently selected from hydrogen, C₁₋₆ alkyl, C₇₋₁₂phenylalkyl, substituted C₇₋₁₂ phenylalkyl, C₆₋₁₂ cycloalkylalkyl,substituted C₆₋₁₂ cycloalkylalkyl, C₃₋₁₂ cycloalkyl, substituted C₃₋₁₂cycloalkyl, C₆₋₁₂ aryl, and substituted C₆₋₁₂ aryl

“Phenylalkyl” refers to an alkyl group in which one of the hydrogenatoms are replaced with a phenyl group. In certain embodiments ofphenylalkyl, one of the hydrogen atoms of the terminal carbon atom of analkyl group is replaced with a phenyl group. In certain embodiments, thephenylalkyl group is C₇₋₁₂ phenylalkyl, C₇₋₁₀ phenylalkyl, C₇₋₉phenylalkyl, and in certain embodiments, benzyl.

“Substituted” refers to a group in which one or more hydrogen atoms areeach independently replaced with the same or different substituent(s).In certain embodiments, the substituent is selected from halogen,—S(O)₂OH, —S(O)₂, —SH, —SR where R is C₁₋₆ alkyl, —COOH, —NO₂, —NR₂where each R is independently selected from hydrogen and C₁₋₃ alkyl,—CN, ═O, C₁₋₆ alkyl, C₁₋₃ alkyl, —CF₃, —OH, phenyl, C₂₋₆ heteroalkyl,C₅₋₆ heteroaryl, C₁₋₆ alkoxy, and —COR where R is C₁₋₆ alkyl. In certainembodiments, the substituent is chosen from —OH, —NH₂, and C₁₋₃ alkyl.

For purposes of the following description, it is to be understood thatembodiments provided by the present disclosure may assume variousalternative variations and step sequences, except where expresslyspecified to the contrary. Moreover, other than in the examples, orwhere otherwise indicated, all numbers expressing, for example,quantities of ingredients used in the specification and claims are to beunderstood as being modified in all instances by the term “about.”Accordingly, unless indicated to the contrary, the numerical parametersset forth in the following specification and attached claims areapproximations that may vary depending upon the desired properties to beobtained. At the very least, and not as an attempt to limit theapplication of the doctrine of equivalents to the scope of the claims,each numerical parameter should at least be construed in light of thenumber of reported significant digits and by applying ordinary roundingtechniques.

Notwithstanding that the numerical ranges and parameters setting forththe broad scope of the invention are approximations, the numericalvalues set forth in the specific examples are reported as precisely aspossible. Any numerical value, however, inherently contains certainerrors necessarily resulting from the standard variation found in theirrespective testing measurements.

Also, it should be understood that any numerical range recited herein isintended to include all sub-ranges encompassed therein. For example, arange of “1 to 10” is intended to include all sub-ranges between (andincluding) the recited minimum value of about 1 and the recited maximumvalue of about 10, that is, having a minimum value equal to or greaterthan about 1 and a maximum value of equal to or less than about 10.

Reference is now made to certain embodiments of polymers, compositions,and methods. The disclosed embodiments are not intended to be limitingof the claims. To the contrary, the claims are intended to cover allalternatives, modifications, and equivalents.

Multifunctional Sulfur-Containing Polymers

As indicated, certain embodiments provided by the present disclosurerelate to multifunctional sulfur-containing polymers. Sulfur-containingpolymers include polythioethers, polydisulfides, and polymers containingboth thioether and disulfide groups. Polythioether generally refers to apolymer containing at least two thioether groups, e.g., two —C—S—C—groups. Polydisulfide refers to a polymer containing at least twodisulfide groups, e.g., two —C—S—S—C— groups. In addition to at leasttwo thioether and/or disulfide groups, sulfur-containing polymersprovided by the present disclosure comprise at least two formal, acetal,and/or ketal groups, e.g., at least two —O—CR₂—O— groups, where each Ris independently selected from hydrogen, C₁₋₆ alkyl, C₇₋₁₂ phenylalkyl,substituted C₇₋₁₂ phenylalkyl, C₆₋₁₂ cycloalkylalkyl, substituted C₆₋₁₂cycloalkylalkyl, C₃₋₁₂ cycloalkyl, substituted C₃₋₁₂ cycloalkyl, C₆₋₁₂aryl, and substituted C₆₋₁₂ aryl. As used herein, “polymer” refers tooligomers, homopolymers, and copolymers. Unless stated otherwise,molecular weights are number average molecular weights for polymericmaterials indicated as “Mn” as determined, for example, by gelpermeation chromatography using a polystyrene standard in anart-recognized manner.

In certain embodiments, sulfur-containing polymers provided by thepresent disclosure comprise the reaction products of reactantscomprising: (a) a sulfur-containing diol; (b) a polyol containing atleast three (3) hydroxyl groups per polyol molecule; and (c) a reactantselected from an aldehyde, a ketone, and a combination thereof. Thereactants may comprise one or more types of sulfur-containing diol, oneor more types of polyol, and/or one or more types of aldehyde and/orketone.

In certain embodiments of the reaction, the sulfur-containing diolcomprises the structure:

where p is selected from 1 and 2; and each R¹ is independently selectedfrom C₂₋₆ alkanediyl. In certain embodiments of a sulfur-containingdiol, p is 1 and in certain embodiments p is 2. In certain embodimentsof a sulfur-containing diol, each R¹ is the same and in certainembodiments, each R¹ is different. In certain embodiments, each R¹ isselected from C₂₋₅ alkanediyl, C₂₋₄ alkanediyl, C₂₋₃ alkanediyl, and incertain embodiments, each R¹ is ethane-1,2-diyl. In certain embodimentsof the reaction, the sulfur-containing diol comprises asulfur-containing diol selected from 2,2′-thiodiethanol,3,3′-thiobis(propan-1-ol), 4,4′-thiobis(butan-1-ol), and a combinationof any of the foregoing. In certain embodiments of the reaction, thesulfur-containing diol comprises 2,2′-thiodiethanol.

In certain embodiments of the reaction, the sulfur-containing diolcomprises a single type of sulfur-containing diol, and in certainembodiments, comprises a mixture of sulfur-containing diols. A mixtureof sulfur-containing diols may comprise from 5 mol % to 95 mol % of oneor more thioethers (p is 1) and from 95 mol % to 5 mol % of one or moredisulfides (p is 2). In certain embodiments, a mixture ofsulfur-containing diols comprises 50 mol % of one or more thioethers and50 mol % of one or more disulfides. In certain embodiments, a mixture ofsulfur-containing diols comprises from 0 mol % to 30 mol % of one ormore disulfides, and from 100 mol % to 70 mol % of one or morethioethers.

In certain embodiments, a polyol contains at least three hydroxyl groupsper polyol molecule. For example, a polyol may contain from three to tenhydroxyl groups per polyol molecule, from three to eight hydroxyl groupsper polyol molecule, from three to six hydroxyl groups per polyolmolecule, and in certain embodiments, from three to four hydroxyl groupsper polyol molecule. In certain embodiments, a polyol contains fourhydroxyl groups per polyol molecule, and in certain embodiments, apolyol contains three hydroxyl groups per polyol molecule. The polyolmay be a single type of polyol or may be a mixture of different polyolshaving the same or different number of hydroxyl groups per molecule.

In certain embodiments, a polyol comprises a triol of Formula (1):

where each R² is independently C₁₋₆ alkanediyl; and in certainembodiments, a polyol comprises a triol of Formula (2):

where each R² is independently C₁₋₆ alkanediyl. In certain embodimentsof a polyol of Formula (1) and Formula (2), each R² may be independentlyselected from a C₁₋₄ alkanediyl, and in certain embodiments from a C₁₋₃alkanediyl. In certain embodiments, each R² may be the same, and incertain embodiments, each R² may be different. In certain embodiments ofa polyol of Formula (1) and Formula (2), each R² is selected frommethanediyl, ethane-1,2-diyl, propane-1,3-diyl, and in certainembodiments, butane-1,4-diyl.

In certain embodiments of the reaction, reactant (c) is an aldehyde. Incertain embodiments in which reactant (c) is an aldehyde, the aldehydecomprises a C₁₋₆ aldehyde, a C₁₋₄ aldehyde, a C₁₋₃ aldehyde, and incertain embodiments, a C₁₋₂ aldehyde. In certain embodiments, thealdehyde comprises an alkyl and is selected from acetaldehyde,propionaldehyde, isobutyraldehyde, and butyraldehyde. In certainembodiments, the aldehyde is formaldehyde.

In certain embodiments of the reaction, reactant (c) is a ketone. Incertain embodiments in which reactant (c) is a ketone, the ketone hasthe formula C(O)R₂ where each R is independently selected from C₁₋₆alkyl, C₇₋₁₂ phenylalkyl, substituted C₇₋₁₂ phenylalkyl, C₆₋₁₂cycloalkylalkyl, substituted C₆₋₁₂ cycloalkylalkyl, C₃₋₁₂ cycloalkyl,substituted C₃₋₁₂ cycloalkyl, C₆₋₁₂ aryl, and substituted C₆₋₁₂ aryl. Incertain embodiments of a ketone, each R is independently selected frommethyl, ethyl, and propyl. In certain embodiments, a ketone is selectedfrom propan-2-one, butan-2-one, pentan-2-one, pentan-3-one, and3-methylbutan-2-one.

In certain embodiments, a sulfur-containing polymer of Formula (I) isthe reaction products of reactants comprising 2,2′-thiodiethanol andformaldehyde, and is referred to herein as thiodiglycol polythioether orthiodiglycol polyformal.

In embodiments in which the one or more polyols used to formsulfur-containing polymers provided by the present disclosure have thesame number of hydroxyl groups, the sulfur-containing polymer will havea hydroxyl functionality approximately equivalent to that of thepolyols. For example, when a polyol having a hydroxyl functionality ofthree or a mixture of polyols in which each of the polyols in themixture has a hydroxyl functionality of three is used to prepare asulfur-containing polymer, the sulfur-containing polymer will have ahydroxyl functionality of three. In certain embodiments, asulfur-containing polymer may have an average hydroxyl functionality ofthree, four, five, and in certain embodiments, six.

When polyols having different hydroxyl functionalities are used toprepare multifunctional sulfur-containing polymers, the multifunctionalsulfur-containing polymers can exhibit a range of functionalities. Forexample, multifunctional sulfur-containing polymers provided by thepresent disclosure may have an average hydroxyl functionality from 3 to12, from 3 to 9, from 3 to 6, from 3 to 4, and in certain embodiments,from 3.1 to 3.5. In certain embodiments, a sulfur-containing polymerhaving an average hydroxyl functionality from three to four may beprepared by reacting a combination of one or more polyols having ahydroxyl functionality of three and one or more polyols having ahydroxyl functionality of four.

In certain embodiments, sulfur-containing polymers of Formula (I) have ahydroxyl number from 10 to 100, from 20 to 80, from 20 to 60, from 20 to50, and in certain embodiments, from 20 to 40. The hydroxyl number isthe hydroxyl content of the sulfur-containing polymer, and may bedetermined, for example, by acetylating the hydroxyl groups andtitrating the resultant acid against potassium hydroxide. The hydroxylnumber is the weight of potassium hydroxide in milligrams that willneutralize the acid from one gram of the sulfur-containing polymer.

In certain embodiments, a sulfur-containing polymer provided by thepresent disclosure has a number average molecular weight from 200 to6,000 Daltons, from 500 to 5,000 Daltons, from 1,000 to 4,000 Daltons,from 1,500 to 3,500 Daltons, and in certain embodiments, from 2,000Daltons to 3,000 Daltons.

In certain embodiments, a sulfur-containing polymer provided by thepresent disclosure is the reaction products of reactants comprising2,2′-thiodiethanol, formaldehyde, and a triol of Formula (1). In certainembodiments, a sulfur-containing polymer provided by the presentdisclosure is the reaction products of reactants comprising2,2′-thiodiethanol, formaldehyde, and a triol of Formula (2).

The reaction used to prepare a sulfur-containing polymer of Formula (I)may take place in the presence of an acidic catalyst, such as sulfuricacid, sulfonic acid, or a combination thereof. In certain embodiments, asulfonic acid may be used. Examples of sulfonic acids include alkylsulfonic acids such as methane sulfonic acid, ethane sulfonic acidtert-butane sulfonic acid, 2-propane sulfonic acid, and cyclohexylsulfonic acid; alkene sulfonic acids such as α-olefin sulfonic acid,dimerized α-olefin sulfonic acid, and 2-hexene sulfonic acid; aromaticsulfonic acids such as para-toluene sulfonic acids, benzene sulfonicacid, and naphthalene sulfonic acid; and polymer-supported sulfonicacids such as AMBERLYST™ sulfonic acid catalysts available from DowChemical.

In certain embodiments, a multifunctional sulfur-containing polymer hasthe structure of Formula (I):

where each n is an integer selected from 1 to 50; m is an integerselected from 3 to 6; each p is independently selected from 1 and 2;each R¹ is independently selected from C₂₋₆ alkanediyl; each R³ isindependently selected from hydrogen, C₁₋₆ alkyl, C₇₋₁₂ phenylalkyl,substituted C₇₋₁₂ phenylalkyl, C₆₋₁₂ cycloalkylalkyl, substituted C₆₋₁₂cycloalkylalkyl, C₃₋₁₂ cycloalkyl, substituted C₃₋₁₂ cycloalkyl, C₆₋₁₂aryl, and substituted C₆₋₁₂ aryl; and Z represents the core of anm-valent parent polyol Z(OH)_(m). Each R¹ may be the same or may bedifferent, and each R² may be the same or may be different.

In certain embodiments of a sulfur-containing polymer of Formula (I),each R¹ is independently selected from C₂₋₆ alkanediyl, C₂₋₄ alkanediyl,C₂₋₃ alkanediyl, and in certain embodiments, ethane-1,2-diyl. In certainembodiments of a compound of Formula (I), each R¹ is ethane-1,2-diyl.

In certain embodiments of a sulfur-containing polymer of Formula (I),each R³ is independently selected from hydrogen, C₁₋₆ alkyl, C₁₋₄ alkyl,C₁₋₃ alkyl, and C₁₋₂ alkyl. In certain embodiments of a compound ofFormula (I), each R³ is methyl, and in certain embodiments, ethyl. Incertain embodiments of a compound of Formula (I), each R³ is hydrogen,and in certain embodiments, each R³ is selected from hydrogen, methyl,and ethyl. In certain embodiments of a compound of Formula (I), each R¹is ethane-1,2-diyl and each R³ is hydrogen.

In certain embodiments of a sulfur-containing polymer of Formula (I),each R¹ is the same and is selected from C₂₋₃ alkanediyl such asethane-1,2-diyl and propane-1,3-diyl; and each R³ is the same and isselected from hydrogen and C₁₋₃ alkyl such as methyl, ethyl, and propyl.In certain embodiments of a sulfur-containing polymer of Formula (I),each R³ is hydrogen, and in certain embodiments, each R³ is methyl. Incertain embodiments of a sulfur-containing polymer of Formula (I), eachR¹ is ethane-1,2-diyl and each R³ is hydrogen. In certain embodiments ofa sulfur-containing polymer of Formula (I), each R¹ is the same and isselected from ethane-1,2-diyl and propane-1,3-diyl; and each R³ isindependently selected from hydrogen, methyl, and ethyl.

In certain embodiments of a sulfur-containing polymer of Formula (I), nis an integer selected from 1 to 50, an integer selected from 2 to 40,an integer selected from 4 to 30, and in certain embodiments, an integerselected from 7 to 30.

In certain embodiments of a sulfur-containing polymer of Formula (I),each p is the same and is 1, and in certain embodiments, each p is thesame and is 2.

In certain embodiments of a compound of Formula (I), m is 1, m is 2, mis 3, m is 4, m is 5, and in certain embodiments, m is 6.

In certain embodiments of a compound of Formula (I), m is 3 and theparent polyol Z(OH)_(m) is a triol of Formula (1):

where each R² is independently C₁₋₆ alkanediyl, and in certainembodiments, a triol of Formula (2):

where each R² is independently C₁₋₆ alkanediyl. Accordingly, Z has thestructure:

respectively where each R² is independently a C₁₋₄ alkanediyl, and each

represents a bond to the group within the outer parenthesis of Formula(I).

In certain embodiments, a sulfur-containing polymer of Formula (I) has ahydroxyl number from 10 to 100, from 20 to 80, from 20 to 60, from 20 to50, and in certain embodiments, from 20 to 40.

In certain embodiments, a sulfur-containing polymer of Formula (I) has anumber average molecular weight from 200 to 6,000 Daltons, from 500 to5,000 Daltons, from 1,000 to 4,000 Daltons, from 1,500 to 3,500 Daltons,and in certain embodiments, from 2,000 Daltons to 3,000 Daltons.

Terminal-Modified Sulfur-Containing Polymers

Hydroxyl-terminated multifunctional sulfur-containing polymers ofFormula (I) may be derivatized such that the terminal hydroxyl groupsare replaced with a group selected from a vinyl-terminated group, anepoxy-terminated group, an amine-terminated group, a silyl-terminatedgroup, a thiol-terminated group, and an isocyanate terminated group.

In certain embodiments, a terminal-modified sulfur-containing polymercomprises the reaction products of reactants comprising (a) asulfur-containing polymer of Formula (I):

where each n is an integer selected from 1 to 50; m is an integerselected from 3 to 6; each p is independently selected from 1 and 2;each R¹ is independently selected from C₂₋₆ alkanediyl; each R³ isindependently selected from hydrogen, C₁₋₆ alkyl, C₇₋₁₂ phenylalkyl,substituted C₇₋₁₂ phenylalkyl, C₆₋₁₂ cycloalkylalkyl, substituted C₆₋₁₂cycloalkylalkyl, C₃₋₁₂ cycloalkyl, substituted C₃₋₁₂ cycloalkyl, C₆₋₁₂aryl, and substituted C₆₋₁₂ aryl; and Z represents the core of anm-valent parent polyol Z(OH)_(m); and (b) a compound comprising aterminal group selected from a vinyl group, a silyl group, an epoxygroup, and an isocyanate group; and a group that is reactive with theterminal hydroxyl groups of the polymer of Formula (I).

In certain embodiments, a terminal-modified sulfur-containing polymercomprises the reaction products of reactants comprising (a) asulfur-containing polymer of Formula (I):

where each n is an integer selected from 1 to 50; m is an integerselected from 3 to 6; each p is independently selected from 1 and 2;each R¹ is independently selected from C₂₋₆ alkanediyl; each R³ isindependently selected from hydrogen, C₁₋₆ alkyl, C₇₋₁₂ phenylalkyl,substituted C₇₋₁₂ phenylalkyl, C₆₋₁₂ cycloalkylalkyl, substituted C₆₋₁₂cycloalkylalkyl, C₃₋₁₂ cycloalkyl, substituted C₃₋₁₂ cycloalkyl, C₆₋₁₂aryl, and substituted C₆₋₁₂ aryl; and Z represents the core of anm-valent parent polyol Z(OH)_(m); and (b) a compound comprising aterminal group selected from a vinyl group, a silyl group, and an epoxygroup; and a group that is reactive with the terminal hydroxyl groups ofthe polymer of Formula (I).

In certain embodiments, a terminal-modified sulfur-containing polymercomprises the reaction products of reactants comprising (a) asulfur-containing polymer of Formula (I):

where each n is an integer selected from 1 to 50; m is an integerselected from 3 to 6; each p is independently selected from 1 and 2;each R¹ is independently selected from C₂₋₆ alkanediyl; each R³ isindependently selected from hydrogen, C₁₋₆ alkyl, C₇₋₁₂ phenylalkyl,substituted C₇₋₁₂ phenylalkyl, C₆₋₁₂ cycloalkylalkyl, substituted C₆₋₁₂cycloalkylalkyl, C₃₋₁₂ cycloalkyl, substituted C₃₋₁₂ cycloalkyl, C₆₋₁₂aryl, and substituted C₆₋₁₂ aryl; and Z represents the core of anm-valent parent polyol Z(OH)_(m); and (b) a compound comprising aterminal group selected from a vinyl group, a silyl group, and an epoxygroup; and a group that is reactive with the terminal hydroxyl groups ofthe polymer of Formula (I).

In certain embodiments of a terminal-modified sulfur-containing polymer,the terminal group is a vinyl group and the compound comprising aterminal vinyl group is selected from an ethylenically unsaturatedmonoisocyanate and an ethylenically unsaturated alcohol.

An ethylenically unsaturated monoisocyanate includes ethylenicallyunsaturated aromatic monoisocyanates and ethylenically unsaturatedaliphatic monoisocyanates. Examples of ethylenically unsaturatedmonoisocyanates include vinyl isocyanate, allyl isocyanate,3-isocyanato-2-methyl-2-propene, methacryloyl isocyanate,isocyanatoethyl methacrylate, vinylbenzyl isocyanate,3-isocyanato-1-butene, 3-isocyanato-3-methyl-1-butene,4-isocyanato-2-methyl-1-butene, 4-isocyanato-3,3-dimethyl-1-butene,4-isocyanato-4-methyl-1-pentene, and 5-isocyanato-1-pentene,2-isocyanatoethyl methacrylate, and dimethyl-meta-isopropenylbenzylisocyanate (TMI). In certain embodiments, an ethylenically unsaturatedmonoisocyanate is selected from vinyl isocyanate, allyl isocyanate, andmethyacryloyl isocyanate. In certain embodiments, an ethylenicallyunsaturated aliphatic monoisocyanate is selected from C₂₋₁₀ alkenylisocyanate, C₂₋₈ alkenyl isocyanate, C₂₋₆ alkenyl isocyanate, and incertain embodiments, C₂₋₃ alkenyl isocyanate.

Examples of ethylenically unsaturated alcohols include, for example,allyl alcohol, 3-buten-1-ol, 3-buten-2-ol, ethylene glycol monovinylether, ethylene glycol monoallyl ether, diethylene glycol monoallylether, glycerin monoallyl ether, trimethylolethane monoallyl ether,trimethylolpropane monoallyl ether, polyethylene glycol monoallyl ether,polypropylene glycol monoallyl ether, 1-vinylcyclobutanol,2-vinylcyclobutanol, 3-vinylcyclobutanol, vinylphenol, 2-allyl phenol,4-allylphenol, 4-allyl-2-methoxyphenol, 4-allyl-2,6-dimethoxyphenol,4-(2-propenyl)-1,2-benzenediol, and4-(2,4-dihydroxyphenyl)-3-buten-2-one. In certain embodiments, anethylenically unsaturated alcohol is selected from allyl alcohol,ethylene glycol monoallyl ether, 2-allylphenol, and 4-allylphenol.

In certain embodiments, the compound comprising a vinyl group is anethylenically unsaturated monoisocyanate and is selected from3-isopropenyl-α,α-dimethylbenzyl isocyanate (CAS 2094-99-7) and2-isocyanatoethyl methacrylate.

In certain embodiments of a reaction to form a terminal-modifiedsulfur-containing polymer, the terminal group is a silyl group and thecompound comprising a terminal silyl group is anisocyanatoalkylalkoxysilane. Examples of suitableisocyanatoalkylalkoxysilanes include, for example,isocyanatopropylmethoxysilane, isocyanatopropylmethyldimethoxysilane,isocyanatopropylmethyldiethoxysilane, isocyanatopropyltriethoxysilane,isocyanatopropyltriisopropoxysilane,isocyanatopropylmethyldiisopropoxysilane,isocyanatoneohexyltrimethoxysilane, isocyanatoneohexyldimethoxysilane,isocyanatoneohexyldiethoxysilane, isocyanatoneohexyltriethoxysilane,isocyanatoneohexyltriisopropoxysilane,isocyanatoneohexyldiisopropoxysilane, isocyanatoisoamyltrimethoxysilane,isocyanatoisoamyldimethoxysilane, isocyanatoisoamylmethylsilane,isocyanatoisoamylmethyldiethoxysilane, isocyanatoisoamyltriethoxysilane,isocyanatoisoamyltriisopropoxysilane, andisocyanatoisoamylmethyldiisopropoxysilane. In certain embodiments, theisocyanatoalkyltrialkoxysilane is 3-isocyanatopropyltrimethoxysilane.

In certain embodiments of a reaction to form a terminal-modifiedsulfur-containing polymer, the terminal group is an epoxy group and thecompound comprising a terminal epoxy group is selected from C₁₋₆ epoxyalkanol, C₁₋₆ epoxy haloalkane, and a combination thereof. Examples ofsuitable C₁₋₆ alkanol epoxides include oxirane-2-ol,oxirane-2-ylmethanol, and 2-(oxirane-2-yl)ethanol. Examples of suitableC₁₋₆ epoxy haloalkanes include, for example, 2-(chloromethyl)oxirane and2-(2-chloroethyl)oxirane.

In certain embodiments, a terminal-modified sulfur-containing polymercomprises the reaction products of reactants comprising (a) and (b),where (a) comprises the reaction products of reactants comprising (i)and (ii), where (i) comprises a sulfur-containing polymer of Formula(I), where each n is an integer selected from 1 to 50; m is an integerselected from 3 to 6; each p is independently selected from 1 and 2;each R¹ is independently selected from C₂₋₆ alkanediyl; each R³ isindependently selected from hydrogen, C₁₋₆ alkyl, C₇₋₁₂ phenylalkyl,substituted C₇₋₁₂ phenylalkyl, C₆₋₁₂ cycloalkylalkyl, substituted C₆₋₁₂cycloalkylalkyl, C₃₋₁₂ cycloalkyl, substituted C₃₋₁₂ cycloalkyl, C₆₋₁₂aryl, and substituted C₆₋₁₂ aryl; and Z represents the core of anm-valent parent polyol Z(OH)_(m); and (ii) comprises a first compoundselected from a diisocyanate, an ethylenically unsaturatedmonoisocyanate, and a tosylate; and (b) comprises a second compoundcomprising a terminal group selected from a vinyl group, a silyl group,and an epoxy group; and a group selected from a group that is reactivewith an isocyanate group, a group that is reactive with an ethylenicallyunsaturated group, and a group that is reactive with a tosylate.

In certain embodiments, an amine-terminated sulfur-containing polymercomprises the reaction products of reactants comprising (a) and (b),where (a) comprises the reaction products of reactants comprising (i)and (ii), where (i) comprises a sulfur-containing polymer of Formula(I):

where each n is an integer selected from 1 to 50; m is an integerselected from 3 to 6; each p is independently selected from 1 and 2;each R¹ is independently selected from C₂₋₆ alkanediyl; each R³ isindependently selected from hydrogen, C₁₋₆ alkyl, C₇₋₁₂ phenylalkyl,substituted C₇₋₁₂ phenylalkyl, C₆₋₁₂ cycloalkylalkyl, substituted C₆₋₁₂cycloalkylalkyl, C₃₋₁₂ cycloalkyl, substituted C₃₋₁₂ cycloalkyl, C₆₋₁₂aryl, and substituted C₆₋₁₂ aryl; and Z represents the core of anm-valent parent polyol Z(OH)_(m); and (ii) comprises a first compoundselected from a diisocyanate, an ethylenically unsaturatedmonoisocyanate, and a tosylate; and (b) comprises a second compoundcomprising an amine group and a group selected from a group that isreactive with an isocyanate group, an ethylenically unsaturated group,and a tosylate.

In certain embodiments, the first compound is a diisocyanate and isselected from, for example, 1,3-phenylene diisocyanate, 1,4-phenylenediisocyanate, 2,6-toluene diisocyanate (2,6-TDI), 2,4-toluenediisocyanate (2,4-TDI), a blend of 2,4-TDI and 2,6-TDI, 1,5-diisocyanatonaphthalene, diphenyl oxide 4,4′-diisocyanate, 4,4′-methylenediphenyldiisocyanate (4,4-MDI), 2,4′-methylenediphenyl diisocyanate (2,4-MDI),2,2′-diisocyanatodiphenylmethane (2,2-MDI), diphenylmethane diisocyanate(MDI), 3,3′-dimethyl-4,4′-biphenylene isocyanate,3,3′-dimethoxy-4,4′-biphenylene diisocyanate,1-[(2,4-diisocyanatophenyl)methyl]-3-isocyanato-2-methyl benzene,2,4,6-triisopropyl-m-phenylene diisocyanate, 4,4-methylene dicyclohexyldiisocyanate (H₁₂MDI), and a combination of any of the foregoing.

In certain embodiments of the reaction to form a terminal-modifiedsulfur-containing polymer, the first compound is an ethylenicallyunsaturated monoisocyanate such as 2-isocyanatoethyl methacrylate.Examples of other ethylenically unsaturated monoisocyanates aredisclosed herein.

In certain embodiments, the first compound is a tosylate such as asulfonyl chloride, for example, p-toluenesulfonyl chloride.

In certain embodiments of a reaction to form a terminal-modifiedsulfur-containing polymer, the second compound comprising a terminalamine group is selected from aniline, an aminoalkyl-substituted aniline,an aminoalkyl, and a sulfur-containing diamine. In certain embodiments,an aminoalkyl-substituted aniline is selected from 4-(aminomethyl)aniline and 4-(aminoethyl)aniline. In certain embodiments an aminoalkylis selected from ethanamine, propan-1-amine, and butan-1-amine. Suitablesulfur-containing diamines include, for example, ETHACURE® 300.

In certain embodiments of a reaction to form a terminal-modifiedsulfur-containing polymer, the second compound is analkyl-aminobenzoate. Examples of suitable alkylaminobenzoates include,for example, methyl 4-aminobenzoate, ethyl 4-aminobenzoate, methyl3-aminobenzoate, ethyl 3-aminobenzoate, methyl 2-aminobenzoate, andethyl 3-aminobenzoate. In certain embodiments, an alkyl-aminobenzoate isethyl 4-aminobenzoate.

In certain embodiments, a thiol-terminated sulfur-containing polymercomprises the reaction products of reactants comprising (a) and (b),where (a) comprises the reaction products of reactants comprising (i)and (ii), where (i) comprises a sulfur-containing polymer of Formula(I):

where each n is an integer selected from 1 to 50; m is an integerselected from 3 to 6; each p is independently selected from 1 and 2;each R¹ is independently selected from C₂₋₆ alkanediyl; each R³ isindependently selected from hydrogen, C₁₋₆ alkyl, C₇₋₁₂ phenylalkyl,substituted C₇₋₁₂ phenylalkyl, C₆₋₁₂ cycloalkylalkyl, substituted C₆₋₁₂cycloalkylalkyl, C₃₋₁₂ cycloalkyl, substituted C₃₋₁₂ cycloalkyl, C₆₋₁₂aryl, and substituted C₆₋₁₂ aryl; and Z represents the core of anm-valent parent polyol Z(OH)_(m); and (ii) comprises a first compoundselected from a diisocyanate, thiourea, an ethylenically unsaturatedmonoisocyanate, and a tosylate; and (b) comprises a mercaptoalkanol when(ii) comprises a diisocyanate; a metal hydrosulfide when (ii) comprisesthiourea; a dithiol when (ii) comprises an ethylenically unsaturatedmonoisocyanate; and a metal hydrosulfide when (ii) comprises a tosylate.

In certain embodiments, the first compound is a diisocyanates includingany of those described herein.

In certain embodiments, the first compound is an ethylenicallyunsaturated monoisocyanate including any of those described herein.

In certain embodiments, the first compound is tosylate including any ofthose described herein such as p-toluenesulfonyl chloride.

In certain embodiments, the second compound is a mercaptoalkanol suchas, for example, C₂₋₆ mercaptoalkanols such as 2-mercaptoethan-1-ol,3-mercaptopropan-1-ol, 4-mercaptobutan-1-ol, 5-mercaptopentan-1-ol, and6-mercaptohexan-1-ol. Examples of suitable dithiols include, forexample, C₂₋₁₀ alkanedithiols such as ethane-1,2-dithiol,propane-1,3-dithiol, butane-1,4-dithiol, pentane-1,5-dithiol, andhexane-1,6-dithiol.

In certain embodiments, the second compound is a metal hydrosulfide suchas sodium hydrosulfide.

In certain embodiments of a reaction to form a terminal-modifiedsulfur-containing polymer, the compound comprising a terminal thiolgroup is selected from a dithiol and an alkyl(bis)oxydialkanethiol. Incertain embodiments, the second compound is a dithiol including, forexample, 1,2-ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol,1,3-butanedithiol, 1,4-butanedithiol, 2,3-butanedithiol,1,3-pentanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol,1,3-dimercapto-3-methylbutane, dipentenedimercaptan,ethylcyclohexyldithiol, dimercaptodiethylsulfide, methyl-substituteddimercaptodiethylsulfide, dimethyl-substituted dimercaptodiethylsulfide,dimethyl-substituted dimercaptodiethylsulfide, dimercaptodioxaoctane,and 1,5-dimercapto-3-oxapentane. A dithiol may have one or more pendantgroups selected from C₁₋₄ alkyl, C₁₋₄ alkoxy, and hydroxyl.

In certain embodiments a dithiol is an alkyl(bis)oxydialkane thiol.Alkyl(bis)oxydialkane thiols may have the general formulaHS—R—O—R—O—R—HS, where each R is an alkanediyl such as, for example,C₂₋₆ alkanediyl, C₂₋₄ alkanediyl, or ethane-1,2-diyl. Suitable dithiolsinclude alkyl(bis)oxyalkanedithiols such as1,8-dimercapto-3,6-dioxaoctane (DMDO) or dimercaptodiethylsulfide(DMDS). In certain embodiments, a dithiol is selected fromdimercaptodiethylsulfide (DMDS), dimercaptodioxaoctane (DMDO), and1,5-dimercapto-3-oxapentane.

Other examples of suitable dithiols include compounds of the formulaHS—R—SH where R is a C₂₋₆ alkanediyl, having one or more pendant groups,which can be, for example, hydroxyl groups, C₁₋₆ alkyl groups such asmethyl or ethyl groups; C₁₋₆ alkoxy, C₆₋₈ cycloalkanediyl, C₆₋₁₀alkanecycloalkanediyl, —[—(CH₂)_(s)—X—]_(q)—(CH₂)_(r), or—[—(CH₂)_(s)—X—]_(q)—(CH₂)_(r)— in which at least one —CH₂— unit issubstituted with a methyl group and in which each s is independentlyselected from an integer selected from 2 to 6, each q is independentlyselected from an integer selected from 1 to 5, and each r isindependently selected from an integer selected from 2 to 10. Dithiolsmay include one or more heteroatom substituents in the carbon backbone,for example, dithiols in which X is a heteroatom such as O, S or otherbivalent heteroatom radical, a secondary or tertiary amine group such as—NR—, where R is hydrogen or methyl, or another substituted trivalentheteroatom. In certain embodiments, X is O or S, and in certainembodiments, p and r are equal, and in certain embodiments both p and rare 2. In certain embodiments, X is a bond. Other examples of suitabledithiols are disclosed, for example, in U.S. Pat. No. 6,172,179, whichis incorporated by reference in its entirety.

In certain embodiments of the above terminal-modified sulfur-containingpolymers, the terminal-modified sulfur-containing polymer has a numberaverage molecular weight from 200 to 6,000 Daltons, from 500 to 5,000Daltons, from 1,000 to 5,000 Daltons, from 1,500 to 4,000 Daltons, andin certain embodiments, from 2,000 to 3,600 Daltons.

Certain terminal-modified sulfur-containing polymers provided by thepresent disclosure have the structure of Formula (II):

where each n is an integer selected from 1 to 50; m is an integerselected from 3 to 6; p is independently selected from 1 and 2; each R¹is independently selected from C₂₋₆ alkanediyl; each R³ is independentlyselected from hydrogen, C₁₋₆ alkyl, C₇₋₁₂ phenylalkyl, substituted C₇₋₁₂phenylalkyl, C₆₋₁₂ cycloalkylalkyl, substituted C₆₋₁₂ cycloalkylalkyl,C₃₋₁₂ cycloalkyl, substituted C₃₋₁₂ cycloalkyl, C₆₋₁₂ aryl, andsubstituted C₆₋₁₂ aryl; each R⁵ is —OR^(5′) wherein R^(5′) is selectedfrom a vinyl-terminated group, a silyl-terminated group, anamine-terminated group, an epoxy-terminated group, a thiol-terminatedgroup, and an isocyanate-terminated group; and Z represents the core ofan m-valent parent polyol Z(OH)_(m).

Certain terminal-modified sulfur-containing polymers provided by thepresent disclosure have the structure of Formula (II):

where each n is an integer selected from 1 to 50; m is an integerselected from 3 to 6; p is independently selected from 1 and 2; each R¹is independently selected from C₂₋₆ alkanediyl; each R³ is independentlyselected from hydrogen, C₁₋₆ alkyl, C₇₋₁₂ phenylalkyl, substituted C₇₋₁₂phenylalkyl, C₆₋₁₂ cycloalkylalkyl, substituted C₆₋₁₂ cycloalkylalkyl,C₃₋₁₂ cycloalkyl, substituted C₃₋₁₂ cycloalkyl, C₆₋₁₂ aryl, andsubstituted C₆₋₁₂ aryl; each R⁵ is —OR^(5′) wherein R^(5′) is selectedfrom a vinyl-terminated group, a silyl-terminated group, anamine-terminated group, an epoxy-terminated group, and athiol-terminated group; and Z represents the core of an m-valent parentpolyol Z(OH)_(m).

In certain embodiments of a sulfur-containing polymer of Formula (II),each R¹ is independently selected from C₂₋₆ alkanediyl, C₂₋₄ alkanediyl,C₂₋₃ alkanediyl, and in certain embodiments, ethane-1,2-diyl. In certainembodiments of a sulfur-containing polymer of Formula (II), each R¹ isethane-1,2-diyl.

In certain embodiments of a sulfur-containing polymer of Formula (II),each R³ is independently selected from hydrogen, C₁₋₆ alkyl, C₁₋₄ alkyl,C₁₋₃ alkyl, and in certain embodiments, C₁₋₂ alkyl. In certainembodiments of a sulfur-containing polymer of Formula (II), each R³ ishydrogen, and in certain embodiments, methyl, and in certain embodimentsethyl.

In certain embodiments of a sulfur-containing polymer of Formula (II),each R¹ is the same and is selected from a C₂₋₃ alkanediyl such asethane-1,2-diyl and propane-1,3-diyl; and each R³ is the same and isselected from hydrogen and C₁₋₃ alkyl such as methyl, ethyl, and propyl.In certain embodiments of a sulfur-containing polymer of Formula (II),each R¹ is ethane-1,2-diyl. In certain embodiments of asulfur-containing polymer of Formula (II), each R³ is hydrogen. Incertain embodiments of a sulfur-containing polymer of Formula (II), eachR¹ is ethane-1,2-diyl and each R³ is hydrogen.

In certain embodiments of a compound of Formula (II), m is 1, m is 2, mis 3, m is 4, m is 5, and in certain embodiments, m is 6.

In certain embodiments of a sulfur-containing polymer of Formula (II)where m is 3, the parent polyol Z(OH)_(m) is a triol of Formula (1):

where each R² is independently C₁₋₆ alkanediyl, and in certainembodiments, a triol of Formula (2):

where each R² is independently C₁₋₆ alkanediyl. Accordingly, in theseembodiments Z has the structure:

respectively, where each R² is independently C₁₋₅ alkanediyl.

In certain embodiments of a sulfur-containing polymer of Formula (II),each n is an integer selected from 1 to 50, an integer selected from 2to 40, an integer selected from 4 to 30, and in certain embodiments, aninteger selected from 7 to 30.

In certain embodiments of a sulfur-containing polymer of Formula (II),each p is the same and is 1, and in certain embodiments, each p is thesame and is 2.

In certain embodiments, a sulfur-containing polymer of Formula (II) hasa number average molecular weight from 200 to 6,000 Daltons, from 500 to5,000 Daltons, from 1,000 to 5,000 Daltons, from 1,500 to 4000 Daltons,and in certain embodiments, from 2,000 to 3,600 Daltons.

In certain embodiments of a sulfur-containing polymer of Formula (II),each R⁵ is the same.

In certain embodiments of a sulfur-containing polymer of Formula (II),each R⁵ is selected from a vinyl-terminated group of Formula (a),Formula (b), Formula (c), Formula (d), and Formula (e):

where each R⁶ is a moiety derived from an ethylenically unsaturatedmonoisocyanate; each R⁷ is selected from C₂₋₆ alkanediyl and C₂₋₆heteroalkanediyl; each R⁸ is selected from hydrogen, C₁₋₆ alkyl, andphenyl; and each R⁹ is selected from C₂₋₆ alkanediyl, C₂₋₆heteroalkanediyl, C₆₋₁₂ arenediyl, substituted C₆₋₁₂ arenediyl, C₆₋₁₂heteroarenediyl, substituted C₆₋₁₂ heteroarenediyl, C₃₋₁₂cycloalkanediyl, substituted C₃₋₁₂ cycloalkanediyl, C₃₋₁₂heterocycloalkanediyl, substituted C₃₋₁₂ heterocycloalkanediyl, C₇₋₁₈alkanearenediyl, substituted C₇₋₁₈ heteroalkanearenediyl, C₄₋₁₈alkanecycloalkanediyl, and substituted C₄₋₁₈ alkanecycloalkanediyl.

In certain embodiments, each R⁶ is derived from an ethylenicallyunsaturated aliphatic monoisocyanate, an ethylenically unsaturatedalicyclic monoisocyanate, and in certain embodiments, an ethylenicallyunsaturated aromatic monoisocyanate.

In certain embodiments of Formula (b) and Formula (d), each R⁷ isselected from C₂₋₄ alkanediyl, C₂₋₃ alkanediyl, and in certainembodiments is selected from ethane-1,2-diyl, propane-1,3-diyl,propane-1,2-diyl, and propane-1,1-diyl. In certain embodiments ofFormula (b) and Formula (d), each R⁷ is selected from ethane-1,2-diyland propane-1,3-diyl.

In certain embodiments of Formula (b), Formula (c), Formula (d), andFormula (e), each R⁸ is selected from hydrogen, methyl, ethyl,isopropyl, and n-propyl.

In certain embodiments of Formula (e), each R⁹ is selected from C₂₋₆alkanediyl, C₆₋₁₂ arenediyl, substituted C₆₋₁₂ arenediyl, C₃₋₁₂cycloalkanediyl, substituted C₃₋₁₂ cycloalkanediyl, C₇₋₁₈alkanearenediyl, substituted C₇₋₁₈ alkanearenediyl, C₄₋₁₈alkanecycloalkanediyl, and substituted C₄₋₁₈ alkanecycloalkanediyl. Incertain embodiments of Formula (e), each R⁹ is the same and is selectedfrom methane-diyl, ethane-1,2-diyl, and propane-1,2-diyl. In certainembodiments of Formula (e), each R⁹ is C₂₋₅ alkanediyl, C₂₋₄ alkanediyl,C₂₋₃ alkanediyl, and in certain embodiments, ethane-1,2-diyl.

In certain embodiments of sulfur-containing polymers of Formula (II),each R⁵ is selected from a silyl-terminated group of Formula (f) andFormula (g):

where each R⁶ is derived from an ethylenically unsaturatedmonoisocyanate; each R¹⁰ is independently selected from C₁₋₆ alkyl, C₁₋₆alkoxy, C₅₋₆ cycloalkyl, C₆₋₁₂ cycloalkylalkyl, phenyl, and C₇₋₁₂phenylalkyl; wherein at least one R¹⁰ is C₁₋₆ alkoxy; and each R¹¹ isC₁₋₆ alkanediyl.

In certain embodiments of Formula (g), each R¹¹ is selected frommethane-diyl, ethane-1,2-diyl, and propane-1,2-diyl. In certainembodiments of Formula (f) and Formula (g), each R¹⁰ is the same and isselected from methoxy, ethoxy, and propoxy. In certain embodiments ofFormula (f) and Formula (g), the silyl-terminal group is atrialkoxysilane, in certain embodiments, a dialkoxysilane, and incertain embodiments, a monoalkoxysilane.

In certain embodiments of sulfur-containing polymers of Formula (II),each R⁵ is selected from an amine-terminated group of Formula (h),Formula (i), Formula (j), Formula (k), Formula (l), and Formula (m):

where each R⁶ is selected from a group derived from a diisocyanate and agroup derived from an ethylenically unsaturated monoisocyanate; each R⁷is selected from a bond and C₂₋₆ alkanediyl; each R⁹ is selected fromC₂₋₆ alkanediyl, C₂₋₆ heteroalkanediyl, C₆₋₁₂ arenediyl, substitutedC₆₋₁₂ arenediyl, C₆₋₁₂ heteroarenediyl, substituted C₆₋₁₂heteroarenediyl, C₃₋₁₂ cycloalkanediyl, substituted C₃₋₁₂cycloalkanediyl, C₃₋₁₂ heterocycloalkanediyl, substituted C₃₋₁₂heterocycloalkanediyl, C₇₋₁₈ alkanearenediyl, substituted C₇₋₁₈heteroalkanearenediyl, C₄₋₁₈ alkanecycloalkanediyl, and substitutedC₄₋₁₈ alkanecycloalkanediyl; and each R¹² is selected from hydrogen,C₁₋₆ alkyl, C₆₋₁₂ aryl, substituted C₆₋₁₂ aryl, C₃₋₁₂ cycloalkyl,substituted C₃₋₁₂ cycloalkyl, C₇₋₁₈ arylalkyl, substituted C₇₋₁₈arylalkyl, C₄₋₁₈ alkylcycloalkyl, and substituted C₄₋₁₈ alkylcycloalkyl.

In certain embodiments of Formula (h), each R⁶ is a group derived from adiisocyanate, and in certain embodiments the group is derived from TDI,ISONATE™ 143L (polycarbodiimide-modified diphenylmethane diisocyanate),DESMODUR® N3400 (1,3-diazetidine-2,4-dione,1,3-bis(6-isocyanatohexyl)-), DESMODUR® (I) (isophorone diisocyanate,IPDI), of DESMODUR® W (H₁₂MDI).

In certain embodiments of Formula (h), each R⁶ is a group derived froman ethylenically unsaturated monoisocyanate, and in certain embodimentsis selected from 2-isocyanatoethyl methacrylate.

In certain embodiments of Formula (j), Formula (k), Formula (l), andFormula (m), each R⁷ is selected from C₂₋₄ alkanediyl, C₂₋₃ alkanediyl,and in certain embodiments is selected from ethane-1,2-diyl,propane-1,3-diyl, propane-1,2-diyl, and propane-1,1-diyl. In certainembodiments of Formula (j), Formula (k), Formula (l), and Formula (m),each R⁷ is selected from ethane-1,2-diyl and propane-1,3-diyl.

In certain embodiments of Formula (k) and Formula (l), each R⁹ isselected from C₂₋₆ alkanediyl, C₆₋₁₂ arenediyl, substituted C₆₋₁₂arenediyl, C₃₋₁₂ cycloalkanediyl, substituted C₃₋₁₂ cycloalkanediyl,C₇₋₁₈ alkanearenediyl, substituted C₇₋₁₈ alkanearenediyl, C₄₋₁₈alkanecycloalkanediyl, and substituted C₄₋₁₈ alkanecycloalkanediyl.

In certain embodiments of Formula (h), Formula (i), Formula (j), Formula(k), Formula (l), and Formula (m), each R¹² is selected from C₁₋₆ alkyl,phenyl, and amino-substituted phenyl. In certain embodiments of Formula(h), Formula (i), Formula (j), Formula (k), Formula (l), and Formula(m), each R¹² is selected from phenyl, methyl, ethyl, propyl,methyl-phenyl, ethyl-phenyl, propyl-phenyl, benzyl, phenethyl,—(CH₂)-aniline, and aminophenyl.

In certain embodiments of a sulfur-containing polymer of Formula (II),each R⁵ is selected from an epoxy-terminated group of Formula (n):

where each R¹¹ is independently C₁₋₆ alkanediyl.

In certain embodiments of Formula (n), each R¹¹ is selected frommethanediyl, ethane-1,2-diyl, and propane-1,3-diyl. In certainembodiments, each R¹¹ is the same and is selected from methanediyl,ethane- 1,2-diyl, and propane-1,3-diyl.

In certain embodiments of a sulfur-containing polymer of Formula (II),each R⁵ is selected from a thiol-terminated group of Formula (o),Formula (p), Formula (q), Formula (r), Formula (s), Formula (t), Formula(u), and Formula (v):

where each R⁶ is selected from a moiety derived from a diisocyanate anda moiety derived from an ethylenically unsaturated monoisocyanate; eachR⁷ is selected from C₂₋₁₄ alkanediyl and C₂₋₁₄ heteroalkanediyl; andeach R⁹ is selected from C₂₋₆ alkanediyl, C₂₋₆ heteroalkanediyl, C₆₋₁₂arenediyl, substituted C₆₋₁₂ arenediyl, C₆₋₁₂ heteroarenediyl,substituted C₆₋₁₂ heteroarenediyl, C₃₋₁₂ cycloalkanediyl, substitutedC₃₋₁₂ cycloalkanediyl, C₃₋₁₂ heterocycloalkanediyl, substituted C₃₋₁₂heterocycloalkanediyl, C₇₋₁₈ alkanearenediyl, substituted C₇₋₁₈heteroalkanearenediyl, C₄₋₁₈ alkanecycloalkanediyl, and substitutedC₄₋₁₈ alkanecycloalkanediyl.

In certain embodiments of Formula (o), each R⁶ is a group derived from adiisocyanate, and in certain embodiments the group is derived from TDI,ISONATE™ 143L (polycarbodiimide-modified diphenylmethane diisocyanate),DESMODUR® N3400 (1,3-diazetidine-2,4-dione,1,3-bis(6-isocyanatohexyl)-), DESMODUR® I (isophorone diisocyanate,IPDI), or DESMODUR® W (H₁₂MDI).

In certain embodiments of Formula (o), each R⁶ is a group derived froman ethylenically unsaturated monoisocyanate, and in certain embodimentsis 2-isocyanatoethyl methacrylate.

In certain embodiments of Formula (o), Formula (p), Formula (q), Formula(s), Formula (t), Formula (u), and Formula (v), each R⁷ is selected fromC₂₋₆ alkanediyl. In certain embodiments of Formula (o), Formula (p),Formula (q), Formula (s), Formula (t), Formula (u), and Formula (v),each R⁷ is selected from —CH₂—S—(CH₂)₂—O—(CH₂)₂—O—(CH₂)₂—,—(CH₂)₂—O—(CH₂)₂—O—(CH₂)₂—, and —(CH₂)₂—S—(CH₂)₂—O—(CH₂)₂—O—(CH₂)₂—.

In certain embodiments of Formula (t) and Formula (u), each R⁹ isselected from C₂₋₆ alkanediyl, C₆₋₁₂ arenediyl, substituted C₆₋₁₂arenediyl, C₃₋₁₂ cycloalkanediyl, substituted C₃₋₁₂ cycloalkanediyl,C₇₋₁₈ alkanearenediyl, substituted C₇₋₁₈ alkanearenediyl, C₄₋₁₈alkanecycloalkanediyl, and substituted C₄₋₁₈ alkanecycloalkanediyl.

In certain embodiments of a sulfur-containing polymer of Formula (II),each R⁵ is selected from an isocyanate-terminated group of Formula (w)and Formula (x):

where each R⁹ is selected from C₂₋₆ alkanediyl, C₂₋₆ heteroalkanediyl,C₆₋₁₂ arenediyl, substituted C₆₋₁₂ arenediyl, C₆₋₁₂ heteroarenediyl,substituted C₆₋₁₂ heteroarenediyl, C₃₋₁₂ cycloalkanediyl, substitutedC₃₋₁₂ cycloalkanediyl, C₃₋₁₂ heterocycloalkanediyl, substituted C₃₋₁₂heterocycloalkanediyl, C₇₋₁₈ alkanearenediyl, substituted C₇₋₁₈heteroalkanearenediyl, C₄₋₁₈ alkanecycloalkanediyl, and substitutedC₄₋₁₈ alkanecycloalkanediyl; and each R¹² is a group derived from adiisocyanate.

In certain embodiments of Formula (w), each R⁹ is selected from C₂₋₆alkanediyl, C₆₋₁₂ arenediyl, substituted C₆₋₁₂ arenediyl, C₃₋₁₂cycloalkanediyl, substituted C₃₋₁₂ cycloalkanediyl, C₇₋₁₈alkanearenediyl, substituted C₇₋₁₈ alkanearenediyl, C₄₋₁₈alkanecycloalkanediyl, and substituted C₄₋₁₈ alkanecycloalkanediyl.

In certain embodiments of Formula (x), each R¹² is a group derived froma diisocyanate, and in certain embodiments is derived from TDI, ISONATE™143L (polycarbodiimide-modified diphenylmethane diisocyanate), DESMODUR®N3400 (1,3-diazetidine-2,4-dione, 1,3-bis(6-isocyanatohexyl)-),DESMODUR® I (isophorone diisocyanate, IPDI), or DESMODUR® W (H₁₂MDI).

Synthesis of Sulfur-Containing Polymers

Multifunctional sulfur-containing polymers provided by the presentdisclosure and precursors thereof may be prepared by a number of methodsknown to those skilled in the art, including those described in theexamples herein. For example, to obtain multifunctionalsulfur-containing polymers of Formula (I), a sulfur-containing diol, apolyol containing at least three hydroxyl groups per polyol molecule,and an aldehyde may be reacted in an organic solvent in the presence ofa sulfonic acid such as AMBERLYST™ 15 to provide the correspondingmultifunctional sulfur-containing polymer of Formula (I).

Synthesis of Terminal-Modified Multifunctional Sulfur-Containing PolymerDerivatives

Terminal-modified multifunctional sulfur-containing polymers provided bythe present disclosure and precursors thereof may be prepared by anumber of methods known to those skilled in the art, including thosedescribed in the Examples herein. For example, to obtainterminal-modified multifunctional sulfur-containing polymers of Formula(II), a multifunctional sulfur-containing polymer of Formula (I) may bereacted with a compound having appropriate terminal groups and a groupthat is reactive with the terminal hydroxyl group of the polymer ofFormula (I).

For example, to obtain a vinyl-terminated sulfur-containing polymer ofFormula (II), a sulfur-containing polymer of Formula (I) may be reactedwith a compound containing a terminal vinyl group and an isocyanategroup, e.g., an ethylenically unsaturated monoisocyanate, such as TMI,2-isocyanatoethyl, or allyl isocyanate, in the presence of dibutyltindilaurate and benzyl chloride at 76° C. As a further example, asulfur-containing polymer of Formula (I) may be reacted with analkane-ol such as 3-butene-1-ol and an aldehyde such as formaldehyde inthe presence of a sulfonic acid (e.g., 4.7 meq/g H⁺) such as AMBERLYST™15 in an organic solvent such as toluene to provide a vinyl-terminatedsulfur-containing polymer of Formula (II).

Silyl-terminated sulfur-containing polymers of Formula (II) may beprepared, for example, by reacting a sulfur-containing polymer ofFormula (I) with an isocyanatoalkyltrialkoxysilane such as a3-isocyanatopropyltrimethoxysilane or 3-isocyanatopropylethoxysilane inthe presence of dibutyltin dilaurate at a temperature of 76° C. toprovide the corresponding silyl-terminated sulfur-containing polymer ofFormula (II).

Epoxy-terminated sulfur-containing polymers of Formula (II) may beprepared, for example, by reacting a sulfur-containing polymer ofFormula (I) in the presence of a monoepoxide such as epichlorohydrin toprovide the corresponding epoxy-terminated sulfur-containing polymer ofFormula (II).

Amine-terminated sulfur-containing polymers of Formula (III) may beprepared, for example, by reacting a vinyl-terminated sulfur-containingpolymer Formula (II)) with aniline, an amino-substituted aniline such as4-(aminomethyl)aniline, or an alkylamine such as n-butylamine,optionally in the presence of a catalyst such as1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), in an organic solvent toprovide the corresponding amine-terminated sulfur-containing polymer ofFormula (III). Alternatively, amine-terminated sulfur-containingpolymers of Formula (III) may be obtained by reacting anisocyanate-terminated sulfur-containing polymer of Formula (II) with adiamine such as 4-(aminomethyl)aniline to provide the correspondingamine-terminated sulfur-containing polymer of Formula (III)Amine-terminated sulfur-containing polymers of Formula (III) may also beobtained by reacting a sulfur-containing polymer of Formula (I) with anamino-substituted benzoate such as ethyl-4-aminobenzoate in the presenceof Bu₂SnO or NaOMe at elevated temperature to provide the correspondingamine-terminated sulfur-containing polymer of Formula (III).Amine-terminated sulfur-containing polymers of Formula (III) may also beprepared by reacting a tosyl-ester of a sulfur-containing polymer ofFormula (III) with an amine-containing compound such as aniline in anorganic solvent at elevated temperature to provide the correspondingamine terminated sulfur-containing polymer of Formula (III).

Thiol-terminated sulfur-containing polymers of Formula (IV) may beprepared by reacting a vinyl-terminated sulfur-containing polymer ofFormula (IV) such as the 2-isocyanatoethyl methacrylate adduct or theallyl isocyanate adduct as disclosed herein with a dithiol such as DMDO.Thiol-terminated sulfur-containing polymers of Formula (IV) may also beprepared by reacting a tosyl-ester of a sulfur-containing polymer ofFormula (I) with NaSH in the presence of MeN(Bu)₃ ⁺Cl⁻ in water toprovide the corresponding thiol-terminated sulfur-containing polymer ofFormula (IV). Alternatively, a tosyl-ester of a sulfur-containingpolymer of Formula (I) may be reacted with thiourea in the presence ofMeN(Bu)₃ ⁺Cl⁻ in water to provide the tosylate salt of the thioureaadduct, which may then be reacted in the presence of base at elevatedtemperature to provide the corresponding thiol-terminatedsulfur-containing polymer of Formula (IV). Alternatively, to obtainthiol-terminated sulfur-containing polymers of Formula (IV), asulfur-containing polymer of Formula (I) may first be reacted with adiisocyanate such as TDI in the presence of dibutyltin dilaurate at 75°C. to 80° C. to provide the corresponding isocyanate-terminatedsulfur-containing polymer of Formula (IV). The isocyanate-terminatedsulfur-containing polymer of Formula (IV) may then be reacted with amercaptoalkanol such as 2-mercaptoethanol or 3-mercaptopropanol toprovide the corresponding thiol-terminated sulfur-containing polymer ofFormula (IV).

Isocyanate-terminated sulfur-containing polymers of Formula (II) may beprepared, for example, by reacting a sulfur-containing polymer ofFormula (I) with a diisocyanate such as TDI, ISONATE™ 143L(polycarbodiimide-modified diphenylmethane diisocyanate), DESMODUR®N3400 (1,3-diazetidine-2,4-dione, 1,3-bis(6-isocyanatohexyl)-),DESMODUR® I (isophorone diisocyanate, IPDI), or DESMODUR® W (H₁₂MDI),optionally in the presence of a catalyst such as dibutyltin dilaurate,at a temperature from 70° C. to 80° C. Isocyanate-terminatedsulfur-containing polymers may be used as intermediates in the synthesisof other terminal-modified sulfur-containing polymers such as certainamine-terminated and thiol-terminated sulfur-containing polymersprovided by the present disclosure.

Properties of Terminal-Modified Multifunctional Sulfur-ContainingPolymers

In certain embodiments, terminal-modified multifunctionalsulfur-containing polymers provided by the present disclosure are liquidat room temperature. Moreover, in certain embodiments, thesulfur-containing polymers have a viscosity, at 100% solids, of no morethan 500 poise, such as 10 to 300 poise or, in some cases, 100 to 200poise, at a temperature of 25° C. and a pressure of 760 mm Hg determinedaccording to ASTM D-2849 §79-90 using a Brookfield CAP 2000 viscometer.In certain embodiments, the T_(g) (glass transition temperature) ofsulfur-containing polymer provided by the present disclosure is nothigher than −40° C., and in certain embodiments, is not higher than −50°C.

Uses

Multifunctional sulfur-containing polymers provided by the presentdisclosure may be used in compositions, such as sealants, coatings,and/or electrical potting compositions that include one or more of thesulfur-containing polymers provided by the present disclosure. A sealantcomposition refers to a composition capable of producing a film that hasthe ability to resist operational conditions, such as moisture andtemperature, and at least partially block the transmission of materials,such as water, fuel, and other liquid and gases. In certain embodiments,sealant compositions provided by the present disclosure are useful,e.g., as aerospace sealants and as linings for fuel tanks.

In certain embodiments, a composition comprises a hydroxyl-terminatedsulfur-containing polymer of Formula (I) or a sulfur-containing polymerproduced by the reaction of (a) a sulfur-containing diol; (b) a polyolcontaining at least three hydroxyl groups per polyol molecule; and (c) areactant selected from an aldehyde, a ketone, and a combination thereof;a compound having a group that is reactive with hydroxyl groups; and acuring agent. In certain embodiments, a group that is reactive withhydroxyl groups is selected from an isocyanate, an alcohol, and a thiol.

In certain embodiments, a composition comprises a terminal-modifiedsulfur-containing polymer of Formula (II) or a terminal-modifiedsulfur-containing polymer, which is the reaction products of any one ofthe reactions disclosed herein, and at least one curing agent that isreactive with the terminal-modified sulfur-containing polymer.

In certain embodiments, compositions provided by the present disclosurecomprise, in addition to a sulfur-containing polymer of Formula (II), orthe reaction products of a reaction as disclosed herein, one or moreadditional sulfur-containing polymers. A sulfur-containing polymer maybe any polymer having at least one sulfur atom in the repeating unit,including polymeric thiols, polythiols, thioethers, sulfur-containingpolymers, polyformals, and polysulfides. A “thiol,” as used herein,refers to a compound comprising a thiol or mercaptan group, that is, an—SH group, either as the sole functional group or in combination withother functional groups, such as hydroxyl groups, as is the case with,for example, thioglycerols. A polythiol refers to such a compound havingmore than one —SH group, such as a dithiol or higher functionalitypolythiol. Such thiol groups are typically terminal and/or pendant suchthat they have an active hydrogen that is reactive with other functionalgroups. As used herein, the term “polysulfide” refers to any compoundthat comprises a sulfur-sulfur linkage (—S—S—). A polythiol may compriseboth a terminal and/or pendant sulfur (—SH) and a non-reactive sulfuratom (—S— or —S—S—). Thus, the term polythiol generally encompassessulfur-containing polymers and polysulfides. Examples of additionalsulfur-containing polymers useful in compositions provided by thepresent disclosure include, for example, those disclosed in U.S. Pat.Nos. 6,172,179, 6,509,418, and 7,009,032.

In certain embodiments, compositions provided by the present disclosurecomprise a polythioether having the structure:—R¹—[—S—(CH₂)₂—O—[—R²—O—]_(t)—(CH₂)₂—S—R¹—]_(u)—wherein R¹ is selected from a C₂₋₆ alkanediyl, C₆₋₈ cycloalkanediyl,C₆₋₁₀ cycloalkylalkanediyl, —[(—CH₂—)_(s)—X—]_(q)—(—CH₂—)_(r)—, and—[(—CH₂—)_(s)—X—]_(q)—(—CH₂—)_(r)— in which at least one —CH₂— unit issubstituted with a methyl group; R² is selected from C₂₋₆ alkanediyl,C₆₋₈ cycloalkanediyl, C₆₋₁₀ cycloalkylalkanediyl, and—[(—CH₂—)_(s)—X—]_(q)—(—CH₂—)_(r)—; X is selected from O, S, and —NR—,where R is selected from hydrogen and methyl; t is an integer selectedfrom 0 to 10; u is an integer selected from 1 to 60; s is an integerselected from 2 to 6; q is an integer selected from 1 to 5, and r is aninteger selected from 2 to 10. Such polythioethers are described in U.S.Pat. No. 6,172,179, which is incorporated by reference in its entirety.The one or more additional sulfur-containing polymers may bedifunctional or multifunctional, for example, having from 3 to 6terminal groups, or a mixture thereof.

In certain embodiments, compositions provided by the present disclosurecomprise from 10 wt % to 90 wt % of a sulfur-containing polymer providedby the present disclosure, from 20 wt % to 80 wt %, from 30 wt % to 70wt %, and in certain embodiments from 40 wt % to 60 wt %, where wt % isbased on the total weight of all non-volatile components of thecomposition (i.e., the dry weight). In certain embodiments, compositionsprovided by the present disclosure comprise from 10 wt % to 90 wt % of asulfur-containing polymer provided by the present disclosure, from 20 wt% to 90 wt %, from 30 wt % to 90 wt %, from 40 wt % to 90 wt %, from 50wt % to 90 wt %, from 60 wt % to 90 wt %, from 70 wt % to 90 wt %, andin certain embodiments from 80 wt % to 90 wt %, where wt % is based onthe total weight of all non-volatile components of the composition(i.e., the dry weight).

Curing agents suitable in compositions provided by the presentdisclosure include compounds that are reactive with the terminal groupsof the sulfur-containing polymer of Formula (II) or as provided by thereactions disclosed herein, such as compounds that are reactive withhydroxyl groups, vinyl groups, epoxy groups, thiol groups amine groups,or isocyanate groups.

Examples of suitable curing agents that are reactive with hydroxylgroups include diisocyanates and polyisocyanates, examples of which aredisclosed herein.

Examples of suitable curing agents that are reactive with vinyl groupsinclude dithiols and polythiols, examples of which are disclosed herein.

Silyl-terminated sulfur-containing polymers provided by the presentdisclosure hydrolyze in the presence of water inducing selfpolymerization via condensation. It can be appreciated that because thecuring agent for silyl-terminated sulfur-containing polymers may beatmospheric moisture, it is not necessary to include a curing agent to acurable composition containing silyl-terminated sulfur-containingpolymers. Therefore, compositions comprising silyl-terminatedsulfur-containing polymers and a curing agent for the silyl group referto atmospheric moisture. Compositions comprising silyl-terminatedsulfur-containing polymers may further comprise a catalyst. Catalystsfor use with silyl-terminated sulfur-containing polymers includeorganotitanium compounds such as tetraisopropoxy titanium,tetra-tert-butoxy titanium, titaniumdi(isopropoxy)bis(ethylacetoacetate), and titaniumdi(isopropoxy)bis(acetylacetoacetate); organic tin compounds dibutyltindilaurate, dibutyltin bisacetylacetoacetate, and tin octylate; metaldicarboxylates such as lead dioctylate; organozirconium compounds suchas zirconium tetraacetyl acetonate; and organoaluminium compounds suchas aluminum triacetyl-acetonate. Specific examples include diisopropoxybis(ethyl acetoacetonate)titanium, diisopropoxy bis(acetylacetonate)titanium, and dibutoxy bis(methyl acetoacetonate)titanium.

Examples of suitable curing agents that are reactive with epoxy groupsinclude amines such as diethylenetriamine (DTA), triethylenetetramine(TTA), tetraethylenepentamine (TEPA), dipropenediamine (DPDA),diethylaminopropylamine (DEAPA), N-aminoethylpiperazine (N-AEP),isophoronediamine (IPDA), m-xylenediamine, diaminodiphenylmethane (DDM),and diaminodiphenylsulfone (DDS); aromatic amines; ketimine; polyamines;polyamides; phenolic resins; anhydrides such phthalic anhydride,trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, ethylene glycol bistrimellitate, glyceroltristrimellitate, maleic anhydride, tetrahydrophthalic anhydride,methyltetrahydrophthalic anhydride, endomethylene tetrahydrophthalicanhydride; polymercaptans; polysulfides; ultraviolet curing agents suchas diphenyliodinium hexafluorophosphate, triphenylsulfoniumhexafluorophosphate; and other curing agents known to those skilled inthe art.

Examples of suitable curing agents that are reactive with thiol groupsinclude diepoxides.

Examples of suitable curing agents that are reactive with amine groupsinclude isocyanates, diisocyanates, and polymeric polyisocyanates,non-limiting examples of which include polyisocyanates having backbonelinkages selected from urethane linkages (—NH—C(O)—O—), thiourethanelinkages (—NH—C(O)—S—), thiocarbamate linkages (—NH—C(S)—O—),dithiourethane linkages (—NH—C(S)—S—), and combinations of any of theforegoing.

Examples of suitable curing agents that are reactive with isocyanategroups include diamines, polyamines, polythiols, and polyols, includingthose disclosed herein.

Compositions provided by the present disclosure may contain from 90% to150% , from 95% to 125%, and in certain embodiments, from 95% to 105% ofthe stoichiometric amount, where the stoichiometric amount is theproportion of the number reactive isocyanate groups to the number ofgroups reactive with the isocyanate groups. For example, a compositioncontaining the same number of isocyanate groups and amine groups priorto reaction will have a stoichiometric amount of isocyanate groups andamine groups.

Compositions provided by the present disclosure may contain one or moredifferent types of filler. Suitable fillers include those commonly knownin the art, including inorganic fillers, such as carbon black andcalcium carbonate (CaCO₃), and lightweight fillers. Suitable lightweightfillers include, for example, those described in U.S. Pat. No.6,525,168. In certain embodiments, a composition includes 5 wt % to 60wt % of the filler or combination of fillers, 10 wt % to 50 wt %, and incertain embodiments, from 20 wt % to 40 wt %, based on the total dryweight of the composition.

As can be appreciated, the sulfur-containing polymers, curing agents,and fillers employed in a composition, as well as any additives, may beselected so as to be compatible with each other.

Compositions provided by the present disclosure may include one or morecolorants, thixotropic agents, accelerators, retardants, adhesionpromoters, solvents, masking agents, or a combination of any of theforegoing.

As used herein, the term “colorant” means any substance that impartscolor and/or other opacity and/or other visual effect to thecomposition. A colorant can be of any suitable form, such as discreteparticles, dispersions, solutions, and/or flakes. A single colorant or amixture of two or more colorants can be used in a composition.

Examples of colorants include pigments, dyes and tints, such as thoseused in the paint industry and/or listed in the Dry Color ManufacturersAssociation (DCMA), as well as special effect compositions. A colorantmay include, for example, a finely divided solid powder that isinsoluble but wettable under the conditions of use. A colorant may beorganic or inorganic and may be agglomerated or non-agglomerated.Colorants may be incorporated into a composition by use of a grindvehicle, such as an acrylic grind vehicle.

Examples of pigments and/or pigment compositions include carbazoledioxazine crude pigment, azo, monoazo, diazo, naphthol AS, salt type(flakes), benzimidazolone, isoindolinone, isoindoline, polycyclicphthalocyanine, quinacridone, perylene, perinone, diketopyrrolo pyrrole,thioindigo, anthraquinone, indanthrone, anthrapyrimidine, flavanthrone,pyranthrone, anthanthrone, dioxazine, triarylcarbonium, quinophthalonepigments, diketo pyrrolo pyrrole red (DPPBO red), titanium dioxide,carbon black, and combinations of any of the foregoing.

Examples of dyes include, but are not limited to, those that aresolvent- and/or aqueous-based such as phthalo green or blue, iron oxide,bismuth vanadate, anthraquinone, perylene, and quinacridone.

Examples of tints include pigments dispersed in water-based orwater-miscible carriers such as AQUA-CHEM 896 commercially availablefrom Degussa, Inc., CHARISMA COLORANTS and MAXITONER INDUSTRIALCOLORANTS commercially available from Accurate Dispersions division ofEastman Chemical, Inc.

As noted above, a colorant may be in the form of a dispersion including,for example, a nanoparticle dispersion. Nanoparticle dispersions mayinclude one or more highly dispersed nanoparticle colorants and/orcolorant particles that produce a desired visible color and/or opacityand/or visual effect. Nanoparticle dispersions may include colorantssuch as pigments or dyes having a particle size of less than 150 nm,such as less than 70 nm, or less than 30 nm. Nanoparticles may beproduced by milling stock organic or inorganic pigments with grindingmedia having a particle size of less than 0.5 mm. Examples ofnanoparticle dispersions and methods for making them are disclosed inU.S. Pat. No. 6,875,800. Nanoparticle dispersions may also be producedby crystallization, precipitation, gas phase condensation, and/orchemical attrition (i.e., partial dissolution). To minimizere-agglomeration of nanoparticles within the coating, a dispersion ofresin-coated nanoparticles may be used. As used herein, a “dispersion ofresin-coated nanoparticles” refers to a continuous phase in which aredispersed discreet “composite microparticles” that comprise ananoparticle and a resin coating on the nanoparticle. Examples ofdispersions containing resin-coated nanoparticles and methods for makingthem are disclosed in U.S. Pat. No. 7,438,972.

Examples of special effect compositions that may be used in compositionsprovided by the present disclosure include pigments and/or compositionsthat produce one or more appearance effects such as reflectance,pearlescence, metallic sheen, phosphorescence, fluorescence,photochromism, photosensitivity, thermochromism, goniochromism, and/orcolor-change. Additional special effect compositions can provide otherperceivable properties, such as opacity or texture. In certainembodiments, special effect compositions may produce a color shift, suchthat the color of a composition changes when the coating is viewed atdifferent angles. Examples of color effect compositions are disclosed inU.S. Pat. No. 6,894,086. Additional color effect compositions mayinclude transparent coated mica and/or synthetic mica, coated silica,coated alumina, a transparent liquid crystal pigment, a liquid crystalcoating, and/or any composition wherein interference results from arefractive index differential within the material and not because of therefractive index differential between the surface of the material andthe air.

In general, a colorant may comprise from 1 wt % to 65 wt % of acomposition, from 2 wt % to 50 wt %, such as from 3 wt % to 40 wt %, orfrom 5 wt % to 35 wt %, with weight percent based on the total dryweight of the composition.

Thixotropes, for example, silica, may be used in an amount from 0.1 wt %to 5 wt %, based on the total dry weight of the composition.

Cure catalysts known to the art, such as amines, may be present in anamount from 0.1 to 5 weight percent, based on the total weight of thecomposition. Examples of suitable catalysts include1,4-diaza-bicyclo[2.2.2]octane (DABCO®, commercially available from AirProducts, Chemical Additives Division) and DMP-30® (an accelerantcomposition including 2,4,6-tris(dimethylaminomethyl)phenol.

Retardants, such as stearic acid, may be used in an amount from 0.1 wt %to 5 wt % of a composition, based on the total dry weight of thecomposition. Adhesion promoters, may be present in amount from 0.1 wt %to 15 wt % of a composition, based on the total dry weight of thecomposition. Examples of adhesion promoters include phenolics, such asMETHYLON phenolic resin available from Occidental Chemicals, andorganosilanes, such as epoxy, mercapto or amino functional silanes, suchas SILQUEST® A-187 and SILQUEST® A-1100 available from MomentivePerformance Materials. Masking agents, such as pine fragrance or otherscents, which may be useful in masking any low level odor of thecomposition, may be present in an amount from 0.1 wt % to 1 wt %, basedon the total dry weight of the composition.

In certain embodiments, compositions provided by the present disclosuremay comprise a plasticizer that may facilitate the use ofsulfur-containing polymers having a higher glass transition temperature,T_(g), than would ordinarily be useful in an aerospace sealant. Forexample, use of a plasticizer may effectively reduce the T_(g) of acomposition, and thereby increase the low-temperature flexibility of thecured polymerizable composition beyond that which would be expected onthe basis of the T_(g) of the sulfur-containing polymers alone.Plasticizers suitable in certain embodiments of the compositionsinclude, for example, phthalate esters, chlorinated paraffins, andhydrogenated terphenyls. A plasticizer or combination of plasticizersmay constitute from 1 wt % to 40 wt % of a composition, or from 1 wt %to 10 wt % of a composition. In certain embodiments, a composition maycomprise one or more organic solvents, such as isopropyl alcohol, in anamount, for example, from 0 wt % to 15 wt %, from 0 wt % to 10 wt %, orfrom 0 wt % to 5 wt %, based on the non-dry weight of the composition.

In certain embodiments, compositions provided by the present disclosureare substantially free or, in some cases, completely free, of anysolvent, such as an organic solvent or an aqueous solvent, i.e., water.Stated differently, in certain embodiments, compositions provided by thepresent disclosure are substantially 100% solids.

In certain embodiments, compositions, such as sealant compositions, maybe provided as multi-pack compositions, such as two-pack compositions,wherein one package comprises one or more sulfur-containing polymersprovided by the present disclosure and a second package comprises one ormore curing agents for the one or more sulfur-containing polymers.Additives and/or other materials may be added to either package asdesired or necessary. The two packages may be combined and mixed priorto use. In certain embodiments, the pot life of the mixedsulfur-containing polymer and curing agent is at least 30 minutes, atleast 1 hour, at least 2 hours, and in certain embodiments, more than 2hours, where pot life refers to the period of time the compositionremains suitable for use as a sealant after mixing.

Compositions provided by the present disclosure may be applied to any ofa variety of substrates. Examples of substrates to which a compositionmay be applied include titanium, stainless steel, and aluminum, whichmay be anodized, primed, organic-coated or chromate-coated; epoxy;urethane; graphite; fiberglass composite; KEVLAR®; acrylics; andpolycarbonates.

Compositions provided by the present disclosure may be applied directlyonto the surface of a substrate or over an underlayer by any suitablecoating process known to those of ordinary skill in the art.

In certain embodiments, compositions provided by the present disclosureare fuel-resistant. As used herein, the term “fuel resistant” means thata composition, when applied to a substrate and cured, can provide acured product, such as a sealant, that has a percent volume swell of notgreater than 40%, in some cases not greater than 25%, in some cases notgreater than 20%, in yet other cases not more than 10%, after immersionfor one week at 140° F. (60° C.) and ambient pressure in Jet ReferenceFluid (JRF) Type I according to methods similar to those described inASTM D792 (American Society for Testing and Materials) or AMS 3269(Aerospace Material Specification, Jet Reference Fluid JRF Type I, asemployed for determination of fuel resistance, has the followingcomposition (see AMS 2629, issued Jul. 1, 1989, §3.1.1 etc., availablefrom SAE (Society of Automotive Engineers)): toluene: 28±1% by volume;cyclohexane (technical): 34±1% by volume; isooctane: 38±1% by volume;and tertiary dibutyl disulfide: 1±0.005% by volume.

In certain embodiments, compositions provide a cured product, such as asealant, exhibiting a tensile strength of at least 400 psi and anelongation of at least 100% when measured in accordance with theprocedure described in AMS 3279, §3.3.17.1, test procedure AS5127/1,§7.7.

In certain embodiments, compositions provide a cured product, such as asealant, exhibiting a lap shear strength of greater than 200 psi and insome cases at least 400 psi when measured according to the proceduredescribed in SAE AS5127/1 paragraph 7.8.

In certain embodiments, a cured sealant comprising a sulfur-containingpolymer provided by the present disclosure meets or exceeds therequirements for aerospace sealants as set forth in AMS 3277.

Furthermore, methods are provided for sealing an aperture utilizing acomposition provided by the present disclosure. These methods comprise,for example, applying a composition provided by the present disclosureto a surface to seal an aperture; and curing the composition. In certainembodiments, a composition may be cured under ambient conditions, whereambient conditions refers to a temperature from 20° C. to 25° C., andatmospheric humidity. In certain embodiments, a composition may be curedunder conditions encompassing a temperature from 0° C. to 100° C. andhumidity from 0% RH to 100% RH. In certain embodiments, a compositionmay be cured at a higher temperature such as at least 30° C., at least40° C., and in certain embodiments, at least 50° C. In certainembodiments, a composition may be cured at room temperature, e.g., 25°C. In certain embodiments, a composition may be cured upon exposure toactinic radiation such as ultraviolet radiation. As will also beappreciated, the methods may be used to seal apertures on aerospacevehicles.

EXAMPLES

Embodiments provided by the present disclosure are further illustratedby reference to the following examples, which describe the synthesis,properties, and uses of certain sulfur-containing polymers. It will beapparent to those skilled in the art that many modifications, both tomaterials, and methods, may be practiced without departing from thescope of the disclosure.

Example 1 Synthesis of Trifunctional Sulfur-Containing Polymer

Thiodiglycol (1,215.81 g), paraformaldehyde (95% purity) (300.63 g),AMBERLYST™ 15 (212.80 g, Dow Chemical Company),1,3,5-tris(2-hydroxyethyl) isocyanurate (13.14 g, Aldrich), and toluene(500 mL) were charged in a 3-liter, 4-neck round-bottom flask. The flaskwas equipped with a heating mantle, thermocouple, temperaturecontroller, and a Dean-Stark adapter fitted with a reflux condenser, adropping funnel and an inlet for nitrogen positive pressure. During thisperiod, collected water was periodically removed from the Dean-Starkadapter. Stirring was started under nitrogen and the batch was heated to120° C. and maintained at 120° C. for about 10 hours. The reactionmixture was then cooled to room temperature and filtered with suctionthrough a coarse-fritted Buchner funnel (600 mL volume) with a 9.0cm-diameter Whatman GF/A filter paper over the frit. The flask andfilter cake were washed with 500 mL toluene. A filtrate was obtained.The filtrate was then stripped in vacuo using a 2-L round bottomed flask(rotary evaporator, 5 torr final vacuum, 90° C. water bath). A yellow,viscous polymer (993.53 g) was obtained. The resulting polyformalpolymer had a hydroxyl number of 25.3 and a viscosity of 214 poise.

Example 2 Synthesis of Trifunctional Sulfur-Containing Polymer

Thiodiglycol (1.209.67 g), paraformaldehyde (95% purity) (300.48 g),AMBERLYST™ 15 (26.18 g, Dow Chemical Company),1,3,5-tris(2-hydroxyethyl) isocyanurate (20.9 g, Aldrich), and toluene(500 mL) were charged in a 3-liter ,4-neck round-bottom flask. The flaskwas equipped with a heating mantle, thermocouple, temperaturecontroller, and a Dean-Stark adapter fitted with a reflux condenser, adropping funnel and an inlet for nitrogen positive pressure. During thisperiod, collected water was periodically removed from the Dean-Starkadapter. Stirring was started under nitrogen and the batch was heated to120° C. and maintained at 120° C. for about 10 hours. The reactionmixture was then cooled to room temperature and filtered with suctionthrough a coarse-fritted Buchner funnel (600 mL volume) with a 9.0 cmdiameter Whatman GF/A filter paper over the frit. The flask and filtercake were washed with 500 mL toluene. A filtrate was obtained. Thefiltrate was then stripped in vacuo using a 2-L round bottomed flask(rotary evaporator, 5 torr final vacuum, 90° C. water bath). A yellow,viscous polymer (953.33 g) was obtained. The resulting polyformalpolymer had a hydroxyl number of 22.8 and a viscosity of 377 poise.

Example 3 Synthesis of Trifunctional Sulfur-Containing Polymer

Thiodiglycol (1,197.45 g), paraformaldehyde (95% purity) (300.83 g),AMBERLYST™ 15 (213.06 g, Dow Chemical Company),1,3,5-tris(2-hydroxyethyl) isocyanurate (52.58 g, Aldrich) and toluene(500 mL) were charged in a 3-liter, 4-neck round-bottom flask. The flaskwas equipped with a heating mantle, thermocouple, temperaturecontroller, and a Dean-Stark adapter fitted with a reflux condenser, adropping funnel and an inlet for nitrogen positive pressure. During thisperiod, collected water was periodically removed from the Dean-Starkadapter. Stirring was started under nitrogen and the batch was heated to120° C. and maintained at 120° C. for about 10 hours. The reactionmixture was then cooled to room temperature and filtered with suctionthrough a coarse-fritted Buchner funnel (600 mL volume) with a 9.0cm-diameter Whatman GF/A filter paper over the frit. The flask andfilter cake were washed with 500 mL toluene. A filtrate was obtained.The filtrate was then stripped in vacuo using a 2-L round bottomed flask(rotary evaporator, 5 torr final vacuum, 90° C. water bath). A yellow,viscous polymer (1,039.64 g) was obtained. The resulting polyformalpolymer had a hydroxyl number of 23.2 and a viscosity of 942 poise.

Example 4 Acrylate-Terminated Sulfur-Containing Polymer

The sulfur-containing polymer of Example 1 (222.40 g) was charged into a500-mL, 4-neck round-bottom flask. The flask was equipped with a mantle,thermocouple, temperature controller, an inlet for nitrogen positivepressure, and a mechanical stirrer (PTFE paddle and bearing). Thepolymer was stirred at ca. 200 rpm and heated to 76.6° C. (170° F.),followed by the addition of isocyanatoethyl methacrylate (15.68 g) and a0.05% solution of dibutyltin dilaurate dissolved in methyl ethyl ketone(2.51 g). The reaction mixture was maintained at 76.6° C. for 5 h andthen cooled to room temperature. The resulting acrylate-terminatedpolymer (222.08 g)had a viscosity of 299 poise.

Example 5 Acrylate-Terminated Sulfur-Containing Polymer

The sulfur-containing polymer of Example 2 (247.26 g) was charged into a500-mL, 4-neck round-bottom flask. The flask was equipped with a mantle,thermocouple, temperature controller, an inlet for nitrogen positivepressure, and a mechanical stirrer (PTFE paddle and bearing). Thepolymer was stirred at ca. 200 rpm and heated to 76.6° C. (170° F.),followed by the addition of isocyanatoethyl methacrylate (15.61 g) and a0.05% solution of dibutyltin dilaurate dissolved in methyl ethyl ketone(2.66 g). The reaction mixture was maintained at 76.6° C. for 5 h andthen cooled to room temperature. The resulting acrylate-terminatedpolymer (242.14 g) had a viscosity of 439 poise.

Example 6 Acrylate-Terminated Sulfur-Containing Polymer

The sulfur-containing polymer of Example 3 (243.71 g) was charged into a500-mL, 4-neck round-bottom flask. The flask was equipped with a mantle,thermocouple, temperature controller, an inlet for nitrogen positivepressure, and a mechanical stirrer (PTFE paddle and bearing). Thepolymer was stirred at ca. 200 rpm and heated to 76.6° C. (170° F.),followed by the addition of isocyanatoethyl methacrylate (15.58 g) and a0.05% solution of dibutyltin dilaurate dissolved in methyl ethyl ketone(2.74 g). The reaction mixture was maintained at 76.6° C. for 5 h andthen cooled to room temperature. The resulting acrylate-terminatedpolymer (226.09 g) had a viscosity of 1,026 poise.

Example 7 TMI-Terminated Sulfur-Containing Polymer

The sulfur-containing polymer in Example 1 (222.6 g) was charged into a500-mL, 4-neck round-bottom flask. The flask was equipped with a mantle,thermocouple, temperature controller, an inlet for nitrogen positivepressure, and a mechanical stirrer (PTFE paddle and bearing). Thepolymer was stirred at ca. 200 rpm and heated to 76.6° C. (170° F.),followed by the addition of 3-isopropenyl-α, α,-dimethylbenzylisocyanate (TMI) (20.25 g, Cytec Industries) and a 0.05% solution ofdibutyltin dilaurate dissolved in methyl ethyl ketone (2.47 g). Thereaction mixture was maintained at 76.6° C. for 6 hours and then cooledto room temperature. The resulting TMI-terminated polymer (217.32) had aviscosity of 378 poise.

Example 8 TMI-Terminated Sulfur-Containing Polymer

The sulfur-containing polymer in Example 3 (243.70 g) was charged into a500-mL, 4-neck round-bottom flask. The flask was equipped with a mantle,thermocouple, temperature controller, an inlet for nitrogen positivepressure, and a mechanical stirrer (PTFE paddle and bearing). Thepolymer was stirred at ca. 200 rpm and heated to 76.6° C. (170° F.),followed by the addition of 3-isopropenyl-α, α,-dimethylbenzylisocyanate (20.18 g, Cytec Industries) and a 0.05% solution ofdibutyltin dilaurate dissolved in methyl ethyl ketone (2.62 g). Thereaction mixture was maintained at 76.6° C. for 6 hours and then cooledto room temperature. The resulting TMI-terminated polymer (230.42 g) hada viscosity of 1.261 poise.

Example 9 Curing of Acrylate-Terminated Sulfur-Containing Polymer

The curing reaction was carried out in a 100-g plastic containerequipped with a lid. The acrylate-terminated sulfur-containing polymerof Example 4 (40.8 g) and IRGACURE® 2022 (0.2 g, 0.5% by weight) weremixed by hand in the container. The container was then placed in a speedmixer (DAC 600 FVZ) and mixed for 1 min at 2,300 rpm. The polymer waspoured over a circular (5 in-diameter) metal lid (pre-treated withValspar Mold Release 225), and placed under ultraviolet (UV) radiationfor 30 sec, after which time the polymer had completely cured. A SuperSix curing unit (Fusion Systems Inc.) was used to provide the UVradiation. The curing unit was equipped with a 300 W H-bulb, whichproduced UV wavelengths ranging from 200 nm to 450 nm. A total dosage of3.103 J/cm² UV energy, measured using a UV power puck (EIT, Inc.,Sterling, Va.) was applied to the polymer composition. A ½ inch-thickdisc of cured polymer was obtained. The hardness of the polymer wasmeasured with a durometer to be 53 Shore A. Hardness was determinedaccording to ASTM D 2240.

Example 10 Curing of Acrylate-Terminated Sulfur-Containing Polymer

The curing reaction was carried out in a 100-g plastic containerequipped with a lid. The acrylate-terminated sulfur-containing polymerof Example 5 (40.8 g) and IRGACURE® 2022 (0.2 g, 0.5% by weight) weremixed by hand in the container. The container was then placed in a speedmixer (DAC 600 FVZ) and mixed for 1 min at 2,300 rpm. The polymer waspoured over a circular (5 in-diameter) metal lid (pre-treated withValspar Mold Release 225), and placed under ultraviolet (UV) radiationfor 30 sec, after which time the polymer had completely cured. A SuperSix curing unit (Fusion Systems Inc.) was used to provide the UVradiation. The curing unit was equipped with a 300 W H-bulb, whichproduced UV wavelengths ranging from 200 nm to 450 nm. A total dosage of3.103 J/cm² UV energy, measured using a UV power puck (EIT, Inc.,Sterling, Va.) was applied to the polymer composition. A ½ inch of curedpolymer was obtained. The hardness of the polymer was measured with adurometer to be 51 Shore A. Hardness was determined according to ASTM D2240.

Example 11 Curing of Acrylate-Terminated Sulfur-Containing Polymer

The curing reaction was carried out in a 100-g plastic containerequipped with a lid. The acrylate-terminated sulfur-containing polymerof Example 6 (40.8 g) and IRGACURE® 2022 (0.2 g, 0.5% by weight) weremixed by hand in the container. The container was then placed in a speedmixer (DAC 600 FVZ) and mixed for 1 min at 2,300 rpm. The polymer waspoured over a circular (5 in-diameter) metal lid (pre-treated withValspar Mold Release 225), and placed under ultraviolet (UV) radiationfor 30 sec, after which time the polymer had completely cured. A SuperSix curing unit (Fusion Systems Inc.) was used to provide the UVradiation. The curing unit was equipped with a 300 W H-bulb, whichproduced UV wavelengths ranging from 200 nm to 450 nm. A total dosage of3.103 J/cm² UV energy, measured using a UV power puck (EIT, Inc.,Sterling, Va.) was applied to the polymer composition. A ½ inch-thickdisc of cured polymer was obtained. The hardness of the polymer wasmeasured with a durometer to be 54 Shore A. Hardness was determinedaccording to ASTM D 2240.

Example 12 Curing of TMI-Terminated Sulfur-Containing Polymer

The curing reaction was performed in a 100-g plastic container equippedwith a lid. The TMI-terminated sulfur-containing polymer described inExample 7 (40.8 g) and IRGACURE® 2022 (0.2 g, 0.5% by weight) were mixedby hand in the container. The container was then placed in a speed mixer(DAC 600 FVZ) and mixed for 1 min at 2,300 rpm. The polymer was pouredover a circular (5 inch-diameter) metal lid (pre-treated with ValsparMold Release 225), and placed under UV light for 60 sec. A Super Sixcuring unit (Fusion Systems Inc.) was used to provide the UV radiation.The curing unit was equipped with a 300 W H-bulb, which produced UVwavelengths ranging from 200 nm to 450 nm. A total dosage of 3.103 J/cm²UV energy, measured using a UV power puck (EIT, Inc., Sterling, Va.) wasapplied to the polymer composition. A 1 mm-thick disc of cured polymerwas obtained.

Example 13 Curing of TMI-Terminated Sulfur-Containing Polymer

The curing reaction was performed in a 100-g plastic container equippedwith a lid. The TMI-terminated sulfur-containing polymer described inExample 8 (40.8 g) and IRGACURE® 2022 (0.2 g, 0.5% by weight) were mixedby hand in the container. The container was then placed in a speed mixer(DAC 600 FVZ) and mixed for 1 min at 2,300 rpm. The polymer was pouredover a circular (5 inch-diameter) metal lid (pre-treated with ValsparMold Release 225), and placed under UV light for 60 sec. A Super Sixcuring unit (Fusion Systems Inc.) was used to provide the UV radiation.The curing unit was equipped with a 300 W H-bulb, which produced UVwavelengths ranging from 200 nm to 450 nm. A total dosage of 3.103 J/cm²UV energy, measured using a UV power puck (EIT, Inc., Sterling, Va.) wasapplied to the polymer composition. A 1 mm-thick disc of cured polymerwas obtained.

Finally, it should be noted that there are alternative ways ofimplementing the embodiments disclosed herein. Accordingly, the presentembodiments are to be considered as illustrative and not restrictive.Furthermore, the claims are not to be limited to the details givenherein, and are entitled their full scope and equivalents thereof.

What is claimed is:
 1. A terminal-modified sulfur-containing polymercomprising the reaction products of reactants comprising: (a) asulfur-containing polymer of Formula (I);

wherein: each n is an integer selected from 1 to 50; m is an integerselected from 3 to 6; each p is 1; each R¹ is C₂₋₆ alkanediyl; each R³is hydrogen; and Z represents the core of an m-valent parent polyolZ(OH)_(m); and (b) a diisocyanate.
 2. The terminal-modifiedsulfur-containing polymer of claim 1, wherein the diisocyanate comprises4,4-methylene dicyclohexyl diisocyanate.
 3. The terminal-modifiedsulfur-containing polymer of claim 1, wherein each R¹ isethane-1,2-diyl.
 4. The terminal-modified sulfur-containing polymer ofclaim 1, wherein the sulfur-containing polymer of Formula (I) comprisesthe reaction products of: (i) a sulfur-containing diol comprising2,2′-thiodiethanol, 3,3′-thiobis(propan-1-ol), 4,4′-thiobis(butan-1-ol),or a combination of any of the foregoing; and (ii) paraformaldehyde. 5.The terminal-modified sulfur-containing polymer of claim 1, comprisingthe reaction product of reactants comprising 2,2′-thiodiethanol andparaformaldehyde.
 6. The terminal-modified sulfur-containing polymer ofclaim 1, wherein the sulfur-containing polymer of Formula (I) has ahydroxyl number from 10 to
 100. 7. The terminal-modifiedsulfur-containing polymer of claim 1, wherein n is an integer selectedfrom 7 to
 30. 8. The terminal-modified sulfur-containing polymer ofclaim 1, wherein Z is selected from a moiety of Formula (1) and a moietyof Formula (2):

wherein each R² is independently C₁₋₆ alkanediyl.
 9. A terminal-modifiedsulfur-containing polymer of Formula (II):

wherein: each n is an integer selected from 1 to 50; m is an integerselected from 3 to 6; each p is 1; each R¹ is C₂₋₆ alkanediyl; each R³is hydrogen; each R⁵ comprises a terminal group derived from adiisocyanate; and Z represents the core of an m-valent parent polyolZ(—OH)_(m).
 10. The terminal-modified sulfur-containing polymer of claim8, wherein the diisocyanate comprises 4,4-methylene dicyclohexyldiisocyanate.
 11. The terminal-modified sulfur-containing polymer ofclaim 8, wherein each R¹ is ethane-1,2-diyl.
 12. A compositioncomprising: the terminal modified sulfur-containing polymer of claim 1;an isocyanate-terminated difunctional terminal modifiedsulfur-containing polyformal; and an isocyanate-terminatedpolythioether.
 13. The composition of claim 11, wherein theisocyanate-terminated polythioether comprises a difunctionalisocyanate-terminated polythioether, a multifunctionalisocyanate-terminated polythioether having from 3 to 6 terminal groups,or a combination thereof.
 14. The composition of claim 11, wherein theisocyanate terminated polythioether comprises the structure:—S—R¹—[—S—(CH₂)₂—O—(R²—O)_(m)—(CH₂)₂—S—R¹—]_(n)—S— wherein, n is aninteger from 0 to 60; each R¹ independently comprises C₂₋₁₀ alkanediyl,C₆₋₈ cycloalkanediyl, C₆₋₁₀ alkanecycloalkanediyl, C₅₋₈heterocycloalkanediyl, —[(—CHR—)_(p)—X—]_(q)—(—CHR—)_(r)— or p is aninteger from 2 to 6; q is an integer from 1 to 5; r is an integer from 2to 10; each R independently comprises hydrogen or methyl; and each Xindependently comprises —O—, —S—, or —NR—, wherein R comprises hydrogenor methyl; m is 0 to 50; and each R² independently comprises C₁₋₁₀alkanediyl, C₆₋₈ cycloalkanediyl, C₆₋₁₄ alkanecycloalkanediyl, or—[(—CHR—)_(p)—X—]_(q)—(—CHR—)_(r)—, wherein p, q, r, R, and X are asdefined for R¹.
 15. The composition of claim 11, further comprising apolyamine curing agent.
 16. A part sealed with the composition of claim14.
 17. A method of sealing a part comprising: applying the compositionof claim 14 to at least a portion of a surface of a part; and curing theapplied composition to seal the part.
 18. A composition comprising: theterminal modified sulfur-containing polymer of claim 8; anisocyanate-terminated difunctional terminal modified sulfur-containingpolyformal; and an isocyanate-terminated polythioether.
 19. Thecomposition of claim 18, wherein the isocyanate-terminated polythioethercomprises a difunctional isocyanate-terminated polythioether, amultifunctional isocyanate-terminated polythioether having from 3 to 6terminal groups, or a combination thereof.
 20. The composition of claim18, wherein the isocyanate terminated polythioether comprises thestructure:—S—R¹—[—S—(CH₂)₂—O—(R²—O)_(m)—(CH₂)₂—S—R¹—]_(n)—S— wherein, n is aninteger from 0 to 60; each R¹ independently comprises C₂₋₁₀ alkanediyl,C₆₋₈ cycloalkanediyl, C₆₋₁₀ alkanecycloalkanediyl, C₅₋₈heterocycloalkanediyl, —[(—CHR—)_(p)—X—]_(q)—(—CHR—)_(r)— or p is aninteger from 2 to 6; q is an integer from 1 to 5; r is an integer from 2to 10; each R independently comprises hydrogen or methyl; and each Xindependently comprises —O—, —S—, or —NR—, wherein R comprises hydrogenor methyl; m is 0 to 50; and each R² independently comprises C₁₋₁₀alkanediyl, C₆₋₈ cycloalkanediyl, C₆₋₁₄ alkanecycloalkanediyl, or—[(—CHR—)_(p)—X—]_(q)—(—CHR—)_(r)—, wherein p, q, r, R, and X are asdefined for R¹.
 21. The composition of claim 18, further comprising apolyamine curing agent.